Electrode binder slurry composition for lithium ion electrical storage devices

ABSTRACT

The present invention provides a slurry composition comprising an electrochemically active material and/or an electrically conductive agent, and a binder comprising a polymer comprising a fluoropolymer dispersed in an organic medium; wherein the organic medium has an evaporation rate less than 10 g/min m 2 , at the dissolution temperature of the fluoropolymer dispersed in the organic medium. The present invention also provides electrodes and electrical storage devices.

FIELD OF THE INVENTION

The invention relates to fluoropolymer slurry compositions that could beused in manufacturing electrodes for use in electrical storage devices,such as batteries.

BACKGROUND OF THE INVENTION

There is a trend in the electronics industry to produce smaller devices,powered by smaller and lighter batteries. Batteries with a negativeelectrode—such as a carbonaceous material, and a positive electrode—suchas lithium metal oxides can provide relatively high power and lowweight.

Fluoropolymers such as polyvinylidene fluoride, because of theirexcellent electrochemical resistance, have been found to be usefulbinders for forming electrodes to be used in electrical storage devices.Typically, the fluoropolymer is dissolved in an organic solvent and theelectrode material, that is, in the case of a positive electrode forlithium ion batteries, the electrochemically active material and acarbonaceous material, is combined with the PVDF solution to form aslurry that is applied to a metal foil or mesh to form the electrode.

The role of the organic solvent is to dissolve fluoropolymer in order toprovide good adhesion between the electrode material particles and themetal foil or mesh upon evaporation of the organic solvent. Currently,the organic solvent of choice is N-methyl-2-pyrrolidone (NMP). PVDFbinders dissolved in NMP provide superior adhesion and aninterconnectivity of all the active ingredients in the electrodecomposition. The bound ingredients are able to tolerate large volumeexpansion and contraction during charge and discharge cycles withoutlosing interconnectivity within the electrodes. Interconnectivity of theactive ingredients in an electrode is extremely important in batteryperformance, especially during charging and discharging cycles, aselectrons must move through the electrode, and lithium ion mobilityrequires interconnectivity within the electrode between particles.

Unfortunately, NMP is a toxic material and presents health andenvironmental issues. It would be desirable to replace NMP as a solventfor PVDF binders. However, NMP is somewhat unique in its ability todissolve PVDF, which is not soluble in many other organic solvents.

To effectively employ PVDF compositions in electrode-forming processesin organic solvent other than NMP, the PVDF must be dispersed (asopposed to dissolved) in the solvent. However, the dispersion must becompatible with current manufacturing practices and provide desiredproperties of the intermediate and final products. Some common criteriainclude: a) stability of the fluoropolymer dispersion having sufficientshelf-life, b) stability of the slurry after admixing theelectrochemically active and/or electroconductive powders with thedispersion, c) appropriate viscosity of the slurry to facilitate goodapplication properties, and d) sufficient interconnectivity within theelectrode.

In addition, after the electrodes are assembled in an electrical storagedevice, the device should be substantially free of moisture andsubstantially free of hydrophilic groups that may attract moisture.

It is therefore an object of the present invention to provide stablePVDF dispersions using alternatives to N-methyl-2-pyrrolidone for use inpreparing electrode-forming compositions, for producing high qualityelectrodes for batteries and other electrical storage devices havinginterconnectivity.

SUMMARY OF THE INVENTION

The present invention provides a slurry composition comprising: (a) anelectrochemically active material; and (b) a binder comprising a polymercomprising a fluoropolymer dispersed in an organic medium; wherein theorganic medium has an evaporation rate less than 10 g/min m², at thedissolution temperature of the fluoropolymer dispersed in the organicmedium.

The present invention also provides a slurry composition comprising: (a)a binder comprising a polymer comprising a fluoropolymer dispersed in anorganic medium; and (b) an electrically conductive agent; wherein theorganic medium has an evaporation rate less than 10 g/min m², at thedissolution temperature of the fluoropolymer dispersed in the organicmedium.

The present invention further provides An electrode comprising (a) anelectrical current collector; and (b) a film formed on the electricalcurrent collector, wherein the film is deposited from a slurrycomposition comprising: (i) an electrochemically active material; (ii)an electrically conductive agent; and (iii) a binder comprising apolymer comprising a fluoropolymer dispersed in an organic medium;wherein the organic medium has an evaporation rate less than 10 g/minm², at the dissolution temperature of the fluoropolymer dispersed in theorganic medium.

The present invention also provides an electrical storage devicecomprising: (a) an electrode comprising: (a) an electrical currentcollector; and (b) a film formed on the electrical current collector,wherein the film is deposited from a slurry composition comprising: (i)an electrochemically active material; (ii) an electrically conductiveagent; and (iii) a binder comprising a polymer comprising afluoropolymer dispersed in an organic medium; wherein the organic mediumhas an evaporation rate less than 10 g/min m², at the dissolutiontemperature of the fluoropolymer dispersed in the organic medium; (b) acounter electrode; and (c) an electrolyte.

DESCRIPTION OF THE DRAWING

FIG. 1 is a graph illustrating the first derivative of Log viscosityversus temperature, wherein the peak maximum is used to determine thedissolution temperature of PVDF in 1,2,3-triacetoxypropane (triacetin)from the abscissa.

DETAILED DESCRIPTION

The present invention is directed to a slurry composition comprising abinder comprising a polymer comprising a fluoropolymer dispersed in anorganic medium, wherein the organic medium has an evaporation rate lessthan 10 g/min m², at the dissolution temperature of the fluoropolymerdispersed in the organic medium. The slurry composition may optionallyfurther comprise a dispersant, an electrochemically active materialand/or an electrically conductive agent.

According to the present invention, the binder comprises a polymercomprising a fluoropolymer dispersed in an organic medium, wherein theorganic medium has an evaporation rate less than 10 g/min m², at thedissolution temperature of the fluoropolymer dispersed in the organicmedium. The fluoropolymer may serve as all or a component of the binderfor the slurry composition.

The fluoropolymer may comprise a (co)polymer comprising the residue ofvinylidene fluoride. A non-limiting example of a (co)polymer comprisingthe residue of vinylidene fluoride is a polyvinylidene fluoride polymer(PVDF). As used herein, the “polyvinylidene fluoride polymer” includeshomopolymers, copolymers, such as binary copolymers, and terpolymers,including high molecular weight homopolymers, copolymers, andterpolymers. Such (co)polymers include those containing at least 50 molepercent, such as at least 75 mole %, and at least 80 mole %, and atleast 85 mole % of the residue of vinylidene fluoride (also known asvinylidene difluoride). The vinylidene fluoride monomer may becopolymerized with at least one comonomer selected from the groupconsisting of tetrafluoroethylene, trifluoroethylene,chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride,pentafluoropropene, tetrafluoropropene, perfluoromethyl vinyl ether,perfluoropropyl vinyl ether and any other monomer that would readilycopolymerize with vinylidene fluoride in order to produce thefluoropolymer of the present invention. The fluoropolymer may alsocomprise a PVDF homopolymer.

The fluoropolymer may comprise a high molecular weight PVDF having aweight average molecular weight of at least 50,000 g/mol, such as atleast 100,000 g/mol, and may range from 50,000 g/mol to 1,500,000 g/mol,such as 100,000 g/mol to 1,000,000 g/mol. PVDF is commerciallyavailable, e.g., from Arkema under the trademark KYNAR from Solvay underthe trademark HYLAR, and from Inner Mongolia 3F Wanhao FluorochemicalCo., Ltd.

The fluoropolymer may comprise a nanoparticle. As used herein, the term“nanoparticle” refers to particles having a particle size of less than1,000 nm. The fluoropolymer may have a particle size of at least 50 nm,such as at least 100 nm, such as at least 250 nm, such as at least 300nm, and may be no more than 900 nm, such as no more than 600 nm, such asno more than 450 nm, such as no more than 400 nm, such as no more than300 nm, such as no more than 200 nm. The fluoropolymer nanoparticles mayhave a particle size of 50 nm to 900 nm, such as 100 nm to 600 nm, suchas 250 nm to 450 nm, such as 300 nm to 400 nm, such as 100 nm to 400 nm,such as 100 nm to 300 nm, such as 100 nm to 200 nm. As used herein, theterm “particle size” refers to average diameter of the fluoropolymerparticles. The particle size referred to in the present disclosure wasdetermined by the following procedure: A sample was prepared bydispersing the fluoropolymer onto a segment of carbon tape that wasattached to an aluminum scanning electron microscope (SEM) stub. Excessparticles were blown off the carbon tape with compressed air. The samplewas then sputter coated with Au/Pd for 20 seconds and was then analyzedin a Quanta 250 FEG SEM (field emission gun scanning electronmicroscope) under high vacuum. The accelerating voltage was set to 20.00kV and the spot size was set to 3.0. Images were collected from threedifferent areas on the prepared sample, and ImageJ software was used tomeasure the diameter of 10 fluoropolymer particles from each area for atotal of 30 particle size measurements that were averaged together todetermine the average particle size.

The fluoropolymer may be present in the binder in amounts of 40% to 100%by weight, such as 40% to 96% by weight, such as 50% to 95% by weight,such as 50% to 90% by weight, such as 70% to 90% by weight, such as 80%to 90% by weight, based on the total weight of the binder solids.

According to the present invention, the slurry composition comprises anorganic medium having an evaporation rate less than 10 g/min m², at thedissolution temperature of the fluoropolymer dispersed in the organicmedium. As used herein, the term “organic medium” refers to a liquidmedium comprising less than 50% by weight water, based on the totalweight of the organic medium. Such organic mediums may comprise lessthan 40% by weight water, or less than 30% by weight water, or less than20% by weight water, or less than 10% by weight water, or less than 5%by weight water, or less than 1% by weight water, or less than 0.1% byweight water, based on the total weight of the organic medium, or may befree of water. Organic solvent(s) comprise more than 50% by weight ofthe organic medium, such as at least 70% by weight, such as at least 80%by weight, such as at least 90% by weight, such as at least 95% byweight, such as at least 99% by weight, such as at least 99.9% byweight, such as 100% by weight, based on the total weight of the organicmedium. The organic solvent(s) may comprise 50.1% to 100% by weight,such as 70% to 100% by weight, such as 80% to 100% by weight, such as90% to 100% by weight, such as 95% to 100% by weight, such as 99% to100% by weight, such as 99.9% to 100% by weight, based on the totalweight of the organic medium.

As discussed above, the organic medium has an evaporation rate less than10 g/min m², at the dissolution temperature of the fluoropolymerdispersed in the organic medium. Evaporation rates may be measured usingASTM D3539 (1996). According to the present invention, the dissolutiontemperature of the fluoropolymer dispersed in the organic medium may bedetermined by measuring complex viscosity of the mixture as a functionof temperature. This technique may be applied to fluoropolymers (inaddition to other types of polymer) mixed in an organic medium where thetotal mass of non-volatile solids content of such mixtures is from 44%to 46%, such as 45% of the total mass of the mixture. Complex viscositymay be measured with an Anton-Paar MCR301 rheometer using a50-millimeter cone and temperature-controlled plate. The complexviscosity of fluoropolymer mixtures is measured over a temperature rangefrom 20° C. to at least 75° C. with a temperature ramp rate of 10° C.per minute, an oscillatory frequency of 1 Hz, and a stress amplitudesetpoint of 90 Pa. The dissolution of fluoropolymer in the organicmedium is indicated by a sharp increase in the complex viscosity astemperature increased. The dissolution temperature is defined as thetemperature at which the rate of change in viscosity with increasingtemperature is highest and is calculated by determining the temperatureat which the first derivative with respect to temperature of the Log₁₀of the complex viscosity reaches a maximum. FIG. 1 is a graphillustrating the first derivative of Log₁₀ complex viscosity versustemperature, wherein the peak maximum is used to determine thedissolution temperature of the fluoropolymer polyvinylidene fluoride(PVDF T-1 from Inner Mongolia 3F Wanhao Fluorochemical Co. Ltd.)dispersed in the organic medium 1,2,3-triacetoxypropane (triacetin) fromthe abscissa. The table below illustrates dissolution temperaturesdetermined according to this method using PVDF T-1 from Inner Mongolia3F Wanhao Fluorochemical Co. Ltd. (PVDF T-1 has a particle size of about330 to 380 nm and a weight average molecular weight of about 130,000 to160,000 g/mol), in various solvents or solvent mixtures as listed.

Solvent Cosolvent % mass of % mass of PVDF % Evaporation rate organicorganic mass of Dissolution at Dissolution Solvent medium Cosolventmedium mixture Temp (° C.) Temp (g/min m²) N-butylpyrrolidone 100 — — 4548 — gamma- 100 — — 45 51 9.31 butyrolactone Isophorone 100 — — 45 7216.59 Triacetin 100 — — 45 76 0.69 Ethyl Acetoacetate 100 — — 45 7637.76 Triethylphosphate 80 Ethyl 20 45 46 — AcetoacetateTriethylphosphate 80 Dowanol ™ 20 45 58 — PM¹ ¹Propylene glycol methylether commercially available from The Dow Chemical Company.

The dissolution temperature of the fluoropolymer dispersed in theorganic medium may be less than 77° C., such as less than 70° C., suchas less than 65° C., such as less than 60° C., such as less than 55° C.,such as less than 50° C. The dissolution temperature of thefluoropolymer dispersed in the organic medium may range from 30° C. to77° C., such as from 30° C. to 70° C., such as 30° C. to 65° C., such as30° C. to 60° C., such as 30° C. to 55° C., such as 30° C. to 50° C. Thedissolution temperature may be measured according to the methoddiscussed above.

The organic medium may comprise, for example, butyl pyrrolidone,trialkyl phosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5 (DBE-5),4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycoldiacetate, dimethyl phthalate, methyl isoamyl ketone, ethyl propionate,1-ethoxy-2-propanol, dipropylene glycol dimethyl ether, saturated andunsaturated linear and cyclic ketones (commercially available as amixture thereof as Eastman™ C-11 Ketone from Eastman Chemical Company),diisobutyl ketone, acetate esters (commercially available as Exxate™1000 from Hallstar), tripropylene glycol methyl ether, diethylene glycolethyl ether acetate, or combinations thereof. The trialkyl phosphate maycomprise, for example, trimethylphosphate, triethylphosphate,tripropylphosphate, tributylphosphate, or the like.

The organic medium may consist essentially of or consist of, forexample, butyl pyrrolidone, trialkyl phosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, cyclohexanone, propylene carbonate, dimethyladipate, propylene glycol methyl ether acetate, dibasic ester (DBE),dibasic ester 5 (DBE-5), 4-hydroxy-4-methyl-2-pentanone (diacetonealcohol), propylene glycol diacetate, dimethyl phthalate, methyl isoamylketone, ethyl propionate, 1-ethoxy-2-propanol, saturated and unsaturatedlinear and cyclic ketones (commercially available as a mixture thereofas Eastman™ C-11 Ketone from Eastman Chemical Company), diisobutylketone, acetate esters (commercially available as Exxate™ 1000 fromHallstar), diethylene glycol ethyl ether acetate, or combinationsthereof.

The organic medium may comprise a primary solvent and a co-solvent thatform a homogenous continuous phase with the fluoropolymer as thedispersed phase. The primary solvent and co-solvent and relevant amountsthereof may be selected to provide a dispersion of the fluoropolymer inthe organic medium at room temperature, i.e., about 23° C. Both theprimary solvent and co-solvent may comprise organic solvent(s). Thefluoropolymer may be soluble in the primary solvent at room temperatureif used alone but use of the co-solvent with the primary solvent mayallow for the fluoropolymer to be stably dispersed in the organicmedium. The primary solvent may comprise, consist essentially of, orconsist of, for example, butyl pyrrolidone, a trialkylphosphate,3-methoxy-N,N-dimethylpropanamide, 1,2,3-triacetoxypropane, orcombinations thereof. The co-solvent may comprise, consist essentiallyof, or consist of, for example, ethyl acetoacetate, gamma-butyrolactone,and/or glycol ethers such as propylene glycol methyl ether, dipropyleneglycol methyl ether, propylene glycol monopropyl ether, diethyleneglycol monobutyl ether, ethylene glycol monohexyl ether, and the like.The primary solvent may be present in an amount of at least 50% byweight, such as at least 65% by weight, such as at least 75 by weight,and may be present in an amount of no more than 99% by weight, such asno more than 90% by weight, such as no more than 85% by weight, based onthe total weight of the organic medium. The primary solvent may bepresent in an amount of 50% to 99% by weight, such as 65% to 90% byweight, such as 75% to 85% by weight, based on the total weight of theorganic medium. The co-solvent may be present in an amount of at least1% by weight, such as at least 10% by weight, such as at least 15% byweight, and may be present in an amount of no more than 50% by weight,such as no more than 35% by weight, such as no more than 25% by weight.The co-solvent may be present in an amount of 1% to 50% by weight, suchas 10% to 35% by weight, such as 15% to 25% by weight, based on thetotal weight of the organic medium.

The organic medium may also have an evaporation rate greater than 80g/min m², at 180° C., such as greater than 90 g/min m², at 180° C., suchas greater than 100 g/min m², at 180° C.

The organic medium may be present in an amount of at least 10% byweight, such as at least 15% by weight, such as at least 20% by weight,such as at least 30% by weight, such as at least 35% by weight, such asat least 40% by weight, and may be present in an amount of no more than80% by weight, such as no more than 70% by weight, such as no more than60% by weight, such as no more than 50% by weight, such as no more than45% by weight, such as no more than 45% by weight, such as no more than40% by weight, such as no more than 35% by weight, such as no more than29% by weight, such as no more than 25% by weight, based on the totalweight of the slurry composition. The organic medium may be present inan amount of such as 20% to 80% by weight, 10% to 70% by weight, such as30% to 70% by weight, such as 35% to 60% by weight, such as 40% to 50%by weight, 15% to 60% by weight, 15% to 50% by weight, 15% to 45% byweight, 15% to 40% by weight, 15% to 35% by weight, 15% to 29% byweight, 15% to 25% by weight, based on the total weight of the slurrycomposition.

The slurry composition may be substantially free, essentially free, orcompletely free of N-Methyl-2-pyrrolidone (NMP). As used herein, theslurry composition is “substantially free” of NMP if NMP is present, ifat all, in an amount of less than 5% by weight, based on the totalweight of the slurry composition. As used herein, the slurry compositionis “essentially free” of NMP if NMP is present, if at all, in an amountof less than 0.3% by weight, based on the total weight of the slurrycomposition. As used herein, the slurry composition is “completely free”of NMP if NMP is not present in the slurry composition, i.e., 0.0% byweight, based on the total weight of the slurry composition.

The slurry composition may be substantially free, essentially free, orcompletely free of ketones such as methyl ethyl ketone, cyclohexanone,isophorone, acetophenone.

The slurry composition may be substantially free, essentially free, orcompletely free of ethers such as the C₁ to C₄ alkyl ethers of ethyleneor propylene glycol.

The slurry composition may optionally further comprise a dispersant. Thedispersant may assist in dispersing the fluoropolymer, and/or, ifpresent, the electrically conductive agent and/or the electrochemicallyactive material in the organic medium. When present, the dispersant maybe a component of the slurry composition binder. The dispersant maycomprise at least one phase that is compatible with the fluoropolymerand/or other components of the slurry composition, such as theelectrically conductive agent or electrochemically active material, ifpresent, and may further comprise at least one phase that is compatiblewith the organic medium. The slurry composition may comprise one, two,three, four or more different dispersants, and each dispersant mayassist in dispersing a different component of the slurry composition.The dispersant may comprise any material having phases compatible withboth the fluoropolymer and/or, if present, the electrically conductiveagent or electrochemically active material, and the organic medium. Asused herein, the term “compatible” means the ability of a material toform a blend with other materials that is and will remain substantiallyhomogenous over time. The fluoropolymer and dispersant may not be boundby a covalent bond. For example, the dispersant may comprise a polymercomprising such phases. The polymer may be in the form of a blockpolymer, a random polymer, or a gradient polymer, wherein the phases ofpresent in the different blocks of the polymer, are randomly includedthroughout the polymer, or are progressively more or less denselypresent along the polymer backbone, respectively. The dispersant maycomprise any suitable polymer to serve this purpose. For example, thepolymer may comprise addition polymers produced by polymerizingethylenically unsaturated monomers, polyepoxide polymers, polyamidepolymers, polyurethane polymers, polyurea polymers, polyether polymers,polyacid polymers, and polyester polymers, among others. The dispersantmay also serve as an additional component of the binder of the slurrycomposition.

The dispersant may comprise functional groups. The functional groups maycomprise, for example, active hydrogen functional groups, heterocyclicgroups, and combinations thereof. As used herein, the term “activehydrogen functional groups” refers to those groups that are reactivewith isocyanates as determined by the Zerewitinoff test described in theJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, page 3181 (1927), andinclude, for example, hydroxyl groups, primary or secondary aminogroups, carboxylic acid groups, and thiol groups. As used herein, theterm “heterocyclic group” refers to a cyclic group containing at leasttwo different elements in its ring such as a cyclic moiety having atleast one atom in addition to carbon in the ring structure, such as, forexample, oxygen, nitrogen or sulfur. Non-limiting examples ofheterocylic groups include epoxides, lactams and lactones. In addition,when epoxide functional groups are present on the addition polymer, theepoxide functional groups on the dispersant may be post-reacted with abeta-hydroxy functional acid. Non-limiting examples of beta-hydroxyfunctional acids include citric acid, tartaric acid, and/or an aromaticacid, such as 3-hydroxy-2-naphthoic acid. The ring opening reaction ofthe epoxide functional group will yield hydroxyl functional groups onthe dispersant.

When acid functional groups are present, the dispersant may have atheoretical acid equivalent weight of at least 350 g/acid equivalent,such as at least 878 g/acid equivalent, such as at least 1,757 g/acidequivalent, and may be no more than 17,570 g/acid equivalent, such as nomore than 12,000 g/acid equivalent, such as no more than 7,000 g/acidequivalent. The dispersant may have a theoretical acid equivalent weightof 350 to 17,570 g/acid equivalent, such as 878 to 12,000 g/acidequivalent, such as 1,757 to 7,000 g/acid equivalent.

As mentioned above, the dispersant may comprise an addition polymer. Theaddition polymer may be derived from, and comprise constitutional unitscomprising the residue of, one or more alpha, beta-ethylenicallyunsaturated monomers, such as those discussed below, and may be preparedby polymerizing a reaction mixture of such monomers. The mixture ofmonomers may comprise one or more active hydrogen group-containingethylenically unsaturated monomers. The reaction mixture may alsocomprise ethylenically unsaturated monomers comprising a heterocyclicgroup. As used herein, an ethylenically unsaturated monomer comprising aheterocyclic group refers to a monomer having at least one alpha, betaethylenic unsaturated group and at least cyclic moiety having at leastone atom in addition to carbon in the ring structure, such as, forexample, oxygen, nitrogen or sulfur. Non-limiting examples ofethylenically unsaturated monomers comprising a heterocyclic groupinclude epoxy functional ethylenically unsaturated monomers, vinylpyrrolidone and vinyl caprolactam, among others. The reaction mixturemay additionally comprise other ethylenically unsaturated monomers suchas alkyl esters of (meth)acrylic acid and others described below.

The addition polymer may comprise a (meth)acrylic polymer that comprisesconstitutional units comprising the residue of one or more (meth)acrylicmonomers. The (meth)acrylic polymer may be prepared by polymerizing areaction mixture of alpha, beta-ethylenically unsaturated monomers thatcomprise one or more (meth)acrylic monomers and optionally otherethylenically unsaturated monomers. As used herein, the term“(meth)acrylic monomer” refers to acrylic acid, methacrylic acid, andmonomers derived therefrom, including alkyl esters of acrylic acid andmethacrylic acid, and the like. As used herein, the term “(meth)acrylicpolymer” refers to a polymer derived from or comprising constitutionalunits comprising the residue of one or more (meth)acrylic monomers. Themixture of monomers may comprise one or more active hydrogengroup-containing (meth)acrylic monomers, ethylenically unsaturatedmonomers comprising a heterocyclic group, and other ethylenicallyunsaturated monomers. The (meth)acrylic polymer may also be preparedwith an epoxy functional ethylenically unsaturated monomer such asglycidyl methacrylate in the reaction mixture, and epoxy functionalgroups on the resulting polymer may be post-reacted with a beta-hydroxyfunctional acid such as citric acid, tartaric acid, and/or3-hydroxy-2-naphthoic acid to yield hydroxyl functional groups on the(meth)acrylic polymer.

The addition polymer may comprise constitutional units comprising theresidue of an alpha, beta-ethylenically unsaturated carboxylic acid.Non-limiting examples of alpha, beta-ethylenically unsaturatedcarboxylic acids include those containing up to 10 carbon atoms such asacrylic acid and methacrylic acid. Non-limiting examples of otherunsaturated acids are alpha, beta-ethylenically unsaturated dicarboxylicacids such as maleic acid or its anhydride, fumaric acid and itaconicacid. Also, the half esters of these dicarboxylic acids may be employed.The constitutional units comprising the residue of the alpha,beta-ethylenically unsaturated carboxylic acids may comprise at least 1%by weight, such as at least 2% by weight, such as at least 5% by weight,and may be no more than 50% by weight, such as no more than 20% byweight, such as no more than 10% by weight, such as no more than 5% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the alpha,beta-ethylenically unsaturated carboxylic acids may comprise 1% to 50%by weight, 2% to 50% by weight, such as 2% to 20% by weight, such as 2%to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising the alpha,beta-ethylenically unsaturated carboxylic acids in an amount of 1% to50% by weight, 2% to 50% by weight, such as 2% to 20% by weight, such as2% to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% byweight, based on the total weight of polymerizable monomers used in thereaction mixture. The inclusion of constitutional units comprising theresidue of an alpha, beta-ethylenically unsaturated carboxylic acids inthe dispersant results in a dispersant comprising at least onecarboxylic acid group which may assist in providing stability to thedispersion.

The addition polymer may comprise constitutional units comprising theresidue of an alkyl esters of (meth)acrylic acid containing from 1 to 3carbon atoms in the alkyl group. Non-limiting examples of alkyl estersof (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkylgroup include methyl (meth)acrylate and ethyl (meth)acrylate. Theconstitutional units comprising the residue of the alkyl esters of(meth)acrylic acid containing from 1 to 3 carbon atoms in the alkylgroup may comprise at least 20% by weight, such as at least 30% byweight, such as at least 40% by weight, such as at least 45% by weight,such as at least 50% by weight, and may be no more than 98% by weight,such as no more than 96% by weight, such as no more than 90% by weight,such as no more than 80% by weight, such as no more than 75% by weight,based on the total weight of the addition polymer. The constitutionalunits comprising the residue of the alkyl esters of (meth)acrylic acidcontaining from 1 to 3 carbon atoms in the alkyl group may comprise 20%to 98% by weight, such as 30% to 96% by weight, such as 30% to 90% byweight, 40% to 90% by weight, such as 40% to 80% by weight, such as 45%to 75% by weight, based on the total weight of the addition polymer. Theaddition polymer may be derived from a reaction mixture comprising thealkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atomsin the alkyl group in an amount of 20% to 98% by weight, such as 30% to96% by weight, such as 30% to 90% by weight, 40% to 90% by weight, suchas 40% to 80% by weight, such as 45% to 75% by weight, based on thetotal weight of polymerizable monomers used in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of an alkyl esters of (meth)acrylic acid containing from 4 to 18carbon atoms in the alkyl group. Non-limiting examples of alkyl estersof (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkylgroup include butyl (meth)acrylate, hexyl (meth)acrylate, octyl(meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate,2-ethylhexyl (meth)acrylate, decyl (meth)acrylate and dodecyl(meth)acrylate. The constitutional units comprising the residue of thealkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atomsin the alkyl group may comprise at least 2% by weight, such as at least5% by weight, such as at least 10% by weight, such as at least 15% byweight, such as at least 20% by weight, and may be no more than 70% byweight, such as no more than 60% by weight, such as no more than 50% byweight, such as no more than 40% by weight, such as no more than 35% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the alkyl esters of(meth)acrylic acid containing from 4 to 18 carbon atoms in the alkylgroup may comprise 2% to 70% by weight, such as 2% to 60% by weight,such as 5% to 50% by weight, 10% to 40% by weight, such as 15% to 35% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising the alkylesters of (meth)acrylic acid containing from 4 to 18 carbon atoms in thealkyl group in an amount of 2% to 70% by weight, such as 2% to 60% byweight, such as 5% to 50% by weight, 10% to 40% by weight, such as 15%to 35% by weight, based on the total weight of polymerizable monomersused in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of a hydroxyalkyl ester. Non-limiting examples of hydroxyalkylesters include hydroxyethyl (meth)acrylate and hydroxypropyl(meth)acrylate. The constitutional units comprising the residue of thehydroxyalkyl ester may comprise at least 0.5% by weight, such as atleast 1% by weight, such as at least 2% by weight, and may be no morethan 30% by weight, such as no more than 20% by weight, such as no morethan 10% by weight, such as no more than 5% by weight, based on thetotal weight of the addition polymer. The constitutional unitscomprising the residue of the hydroxyalkyl ester may comprise 0.5% to30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight,2% to 10% by weight, such as 2% to 5% by weight, based on the totalweight of the addition polymer. The addition polymer may be derived froma reaction mixture comprising the hydroxyalkyl ester in an amount of0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% byweight, 2% to 10% by weight, such as 2% to 5% by weight, based on thetotal weight of polymerizable monomers used in the reaction mixture. Theinclusion of constitutional units comprising the residue of ahydroxyalkyl ester in the dispersant results in a dispersant comprisingat least one hydroxyl group (although hydroxyl groups may be included byother methods). Hydroxyl groups resulting from inclusion of thehydroxyalkyl esters (or incorporated by other means) may react with aseparately added crosslinking agent that comprises functional groupsreactive with hydroxyl groups such as, for example, an aminoplast,phenolplast, polyepoxides and blocked polyisocyanates, or withN-alkoxymethyl amide groups or blocked isocyanato groups present in theaddition polymer when self-crosslinking monomers that have groups thatare reactive with the hydroxyl groups are incorporated into the additionpolymer.

The addition polymer may comprise constitutional units comprising theresidue of an ethylenically unsaturated monomer comprising aheterocyclic group. Non-limiting examples of ethylenically unsaturatedmonomers comprising a heterocyclic group include epoxy functionalethylenically unsaturated monomers, such as glycidyl (meth)acrylate,vinyl pyrrolidone and vinyl caprolactam, among others. Theconstitutional units comprising the residue of the ethylenicallyunsaturated monomers comprising a heterocyclic group may comprise atleast 0.5% by weight, such as at least 1% by weight, such as at least 5%by weight, such as at least 8% by weight, and may be no more than 99% byweight, such as no more than 50% by weight, such as no more than 40% byweight, such as no more than 30% by weight, such as no more than 27% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the ethylenicallyunsaturated monomers comprising a heterocyclic group may comprise 0.5%to 99% by weight, such as 0.5% to 50% by weight, such as 1% to 40% byweight, such as 5% to 30% by weight, 8% to 27% by weight, based on thetotal weight of the addition polymer. The addition polymer may bederived from a reaction mixture comprising the ethylenically unsaturatedmonomers comprising a heterocyclic group in an amount of 0.5% to 50% byweight, such as 1% to 40% by weight, such as 5% to 30% by weight, 8% to27% by weight, based on the total weight of polymerizable monomers usedin the reaction mixture.

As noted above, the addition polymer may comprise constitutional unitscomprising the residue of a self-crosslinking monomer, and the additionpolymer may comprise a self-crosslinking addition polymer. As usedherein, the term “self-crosslinking monomer” refers to monomers thatincorporate functional groups that may react with other functionalgroups present on the dispersant to a crosslink between the dispersantor more than one dispersant. Non-limiting examples of self-crosslinkingmonomers include N-alkoxymethyl (meth)acrylamide monomers such asN-butoxymethyl (meth)acrylamide and N-isopropoxymethyl (meth)acrylamide,as well as self-crosslinking monomers containing blocked isocyanategroups, such as isocyanatoethyl (meth)acrylate in which the isocyanatogroup is reacted (“blocked”) with a compound that unblocks at curingtemperature. Examples of suitable blocking agents includeepsilon-caprolactone and methylethyl ketoxime. The constitutional unitscomprising the residue of the self-crosslinking monomer may comprise atleast 0.5% by weight, such as at least 1% by weight, such as at least 2%by weight, and may be no more than 30% by weight, such as no more than20% by weight, such as no more than 10% by weight, such as no more than5% by weight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the self-crosslinkingmonomer may comprise 0.5% to 30% by weight, such as 1% to 20% by weight,such as 2% to 20% by weight, 2% to 10% by weight, such as 2% to 5% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising theself-crosslinking monomer in an amount of 0.5% to 30% by weight, such as1% to 20% by weight, such as 2% to 20% by weight, 2% to 10% by weight,such as 2% to 5% by weight, based on the total weight of polymerizablemonomers used in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of other alpha, beta-ethylenically unsaturated monomers.Non-limiting examples of other alpha, beta-ethylenically unsaturatedmonomers include vinyl aromatic compounds such as styrene, alpha-methylstyrene, alpha-chlorostyrene and vinyl toluene; organic nitriles such asacrylonitrile and methacrylonitrile; allyl monomers such as allylchloride and allyl cyanide; monomeric dienes such as 1,3-butadiene and2-methyl-1,3-butadiene; and acetoacetoxyalkyl (meth)acrylates such asacetoacetoxyethyl methacrylate (AAEM) (which may be self-crosslinking).The constitutional units comprising the residue of the other alpha,beta-ethylenically unsaturated monomers may comprise at least 0.5% byweight, such as at least 1% by weight, such as at least 2% by weight,and may be no more than 30% by weight, such as no more than 20% byweight, such as no more than 10% by weight, such as no more than 5% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the other alpha,beta-ethylenically unsaturated monomers may comprise 0.5% to 30% byweight, such as 1% to 20% by weight, such as 2% to 20% by weight, 2% to10% by weight, such as 2% to 5% by weight, based on the total weight ofthe addition polymer. The addition polymer may be derived from areaction mixture comprising the other alpha, beta-ethylenicallyunsaturated monomers in an amount of 0.5% to 30% by weight, such as 1%to 20% by weight, such as 2% to 20% by weight, 2% to 10% by weight, suchas 2% to 5% by weight, based on the total weight of polymerizablemonomers used in the reaction mixture.

The monomers and relative amounts may be selected such that theresulting addition polymer has a Tg of 100° C. or less, typically from−50° C. to +70° C., such as −50° C. to 0° C. A lower Tg that is below 0°C. may be desirable to ensure acceptable battery performance at lowtemperature.

The addition polymers may be prepared by conventional free radicalinitiated solution polymerization techniques in which the polymerizablemonomers are dissolved in a second organic medium comprising a solventor a mixture of solvents and polymerized in the presence of a freeradical initiator until conversion is complete. The second organicmedium used to prepare the addition polymer may be the same as theorganic medium present in the slurry composition such that thecomposition of the organic medium is unchanged by addition of theaddition polymer solution. For example, the second organic medium maycomprise the same primary solvent(s) and co-solvent(s) in the sameratios as the organic medium of the slurry composition. Alternatively,the second organic medium used to prepare the addition polymer may bedifferent and distinct from the organic medium of the slurrycomposition. The second organic medium used to produce the additionpolymer may comprise any suitable organic solvent or mixture ofsolvents, including those discussed above with respect to the organicmedium, such as, for example, triethylphosphate.

Examples of free radical initiators are those which are soluble in themixture of monomers such as azobisisobutyronitrile, azobis(alpha,gamma-methylvaleronitrile), tertiary-butyl perbenzoate, tertiary-butylperacetate, benzoyl peroxide, ditertiary-butyl peroxide and tertiaryamyl peroxy 2-ethylhexyl carbonate.

Optionally, a chain transfer agent which is soluble in the mixture ofmonomers such as alkyl mercaptans, for example, tertiary-dodecylmercaptan; ketones such as methyl ethyl ketone, chlorohydrocarbons suchas chloroform can be used. A chain transfer agent provides control overthe molecular weight to give products having required viscosity forvarious coating applications. Tertiary-dodecyl mercaptan is preferredbecause it results in high conversion of monomer to polymeric product.

To prepare the addition polymer, the solvent may be first heated toreflux and the mixture of polymerizable monomers containing the freeradical initiator may be added slowly to the refluxing solvent. Thereaction mixture is then held at polymerizing temperatures so as toreduce the free monomer content, such as to below 1.0 percent andusually below 0.5 percent, based on the total weight of the mixture ofpolymerizable monomers.

For use in the slurry composition of the invention, the dispersantsprepared as described above usually have a weight average molecularweight of about 5000 to 500,000 g/mol, such as 10,000 to 100,000 g/mol,and 25,000 to 50,000 g/mol.

The dispersant may be present in the binder in amounts of 2% to 20% byweight, such as 5% to 15% by weight, based on the total weight of thebinder solids.

As noted above, the slurry composition may optionally further comprise aseparately added crosslinking agent for reaction with the dispersant.The crosslinking agent should be soluble or dispersible in the organicmedium and be reactive with active hydrogen groups of the dispersant,such as the carboxylic acid groups and the hydroxyl groups, if present.Non-limiting examples of suitable crosslinking agents include aminoplastresins, blocked polyisocyanates and polyepoxides.

Examples of aminoplast resins for use as a crossslinking agent are thosewhich are formed by reacting a triazine such as melamine orbenzoguanamine with formaldehyde. These reaction products containreactive N-methylol groups. Usually, these reactive groups areetherified with methanol, ethanol, butanol including mixtures thereof tomoderate their reactivity. For the chemistry preparation and use ofaminoplast resins, see “The Chemistry and Applications of AminoCrosslinking Agents or Aminoplast”, Vol. V, Part II, page 21 ff., editedby Dr. Oldring; John Wiley & Sons/Cita Technology Limited, London, 1998.These resins are commercially available under the trademark MAPRENAL®such as MAPRENAL MF980 and under the trademark CYMIEL® such as CYMEL 303and CYMEL 1128, available from Cytec Industries.

Blocked polyisocyanate crosslinking agents are typically diisocyanatessuch as toluene diisocyanate, 1,6-hexamethylene diisocyanate andisophorone diisocyanate including isocyanato dimers and trimers thereofin which the isocyanate groups are reacted (“blocked”) with a materialsuch as epsilon-caprolactone and methylethyl ketoxime. At curingtemperatures, the blocking agents unblock exposing isocyanatefunctionality that is reactive with the hydroxyl functionalityassociated with the (meth)acrylic polymer. Blocked polyisocyanatecrosslinking agents are commercially available from Covestro as DESMODURBL.

Examples of polyepoxide crosslinking agents are epoxy-containing(meth)acrylic polymers such as those prepared from glycidyl methacrylatecopolymerized with other vinyl monomers, polyglycidyl ethers ofpolyhydric phenols such as the diglycidyl ether of bisphenol A; andcycloaliphatic polyepoxides such as3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate andbis(3,4-epoxy-6-methylcyclohexyl-methyl) adipate.

In addition to promoting the cross-linking of the dispersant, thecrosslinking agents, including those associated with crosslinkingmonomers and separately added crosslinking agents, react with thehydrophilic groups, such as active hydrogen functional groups of thedispersant preventing these groups from absorbing moisture that could beproblematic in a lithium ion battery.

The separately added crosslinker may be present in the binder in amountsof up to 15% by weight, such as 1% to 15% by weight, the % by weightbeing based on the total weight of the binder solids.

The slurry composition may optionally further comprise an adhesionpromoter. The adhesion promoter may comprise a polyvinylidene fluoridecopolymer different than the fluoropolymer described above, anacid-functional polyolefin, or a thermoplastic material.

The polyvinylidene fluoride copolymer adhesion promoter comprisesconstitutional units comprising the residue of vinylidene fluoride andat least one of (i) a (meth)acrylic acid; and/or (ii) a hydroxyalkyl(meth)acrylate. The (meth)acrylic acid may comprise acrylic acid,methacrylic acid, or combinations thereof. The hydroxyalkyl(meth)acrylate may comprise a C₁ to C₅ hydroxyalkyl (meth)acrylate, suchas, for example, hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, or combinations thereof.A commercially available example of such an addition polymer includesSOLEF 5130, available from Solvay. Unlike the fluoropolymer discussedabove, the polyvinylidene fluoride copolymer may be dispersed orsolubilized in the organic medium of the slurry composition.

The acid-functional polyolefin adhesion promoter comprises anethylene-(meth)acrylic acid copolymer, such as an ethylene-acrylic acidcopolymer or an ethylene-methacrylic acid copolymer. Theethylene-acrylic acid copolymer may comprise constitutional unitscomprising 10% to 50% by weight acrylic acid, such as 15% to 30% byweight, such as 17% to 25% by weight, such as about 20% by weight, basedon the total weight of the ethylene-acrylic acid copolymer, and 50% to90% by weight ethylene, such as 70% to 85% by weight, such as 75% to 83%by weight, such as about 80% by weight, based on the total weight of theethylene-acrylic acid copolymer. A commercially available example ofsuch an addition polymer includes PRIMACOR 5980i, available from the DowChemical Company.

The adhesion promoter may be present in the slurry composition in anamount of 10% to 60% by weight, 20% to 60% by weight, such as 30% to 60%by weight, such as 10% to 50% by weight, such as 15% to 40% by weight,such as 20% to 30% by weight, such as 35% to 35% by weight, based on thetotal weight of the binder solids.

The coating film produced from the slurry composition comprising anadhesion promoter may possess improved adhesion to the current collectorcompared to a coating film produced from a slurry composition that doesnot include the adhesion promoter. For example, the use of the coatingfilm resulting from the slurry composition comprising an adhesionpromoter may improve adhesion by at least 50%, such as at least 100%,such as at least 200%, such as at least 300%, such as at least 400%,compared to a coating film produced from a slurry composition that doesnot include the adhesion promoter. As used herein, the term “adhesion”refers to peel strength adhesion as measured by the PEEL STRENGTH TESTMETHOD. According to the PEEL STRENGTH TEST METHOD, adhesion is measuredusing a motorized test stand (EMS-303, available from Mark-10) equippedwith a 10 N force gauge (Series 5, Model M5-2) and a 90° peel stage. Thelateral movement of the 90° peel stage is actively driven at the samerate as the vertical movement of the test stand crosshead, which ensuresa 90° peel angle throughout the entire measurement. A coating onaluminum foil, prepared as described in the Examples section below, iscut into rectangular strips (1.1 inches wide by 11 inches long). Thecoated side of the strips are adhered to a rigid aluminum substrateusing 3M 444 double-sided tape (1-inch wide by 7 inches long), leaving afree end of the foil that was not taped down. The rigid aluminumsubstrate is then fastened to the 90° peel stage, and the free end ofthe foil is secured in the peel stage grips such that a 90° angle isachieved between the instrument crosshead and the peel stage. Thesamples are then peeled at a rate of 50 mm/min for 2 minutes.

The binder typically has a resin solids content of from 30% to 80% byweight, such as 40% to 70% by weight, based on the total weight of thebinder dispersion. As used herein, the term “resin solids” may be usedsynonymously with “binder solids” and include the fluoropolymer and, ifpresent, the dispersant, adhesion promoter, and separately addedcrosslinking agent. As used herein, the term “binder dispersion” refersto a dispersion of the binder solids in the organic medium. Thefluoropolymer may be present in the binder in amounts of 40% to 96% byweight, such as 50% to 90% by weight; the dispersant may be present inamounts of 2% to 20% by weight, such as 5% to 15% by weight; theadhesion promoter may be present in the slurry composition in an amountof 10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% byweight, such as 10% to 50% by weight, such as 15% to 40% by weight, suchas 20% to 30% by weight, such as 35% to 35% by weight; and theseparately added crosslinker may be present in amounts of up to 15% byweight, such as 1% to 15% by weight, the % by weight being based on thetotal weight of the binder solids. The organic medium is present in thebinder dispersion in amounts of 20% to 70% by weight, such as 30% to 60%by weight, based on total weight of the binder dispersion.

The binder solids may be present in the slurry in amounts of 1% to 20%by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry.

The slurry composition may optionally further comprise anelectrochemically active material. The material constituting theelectrochemically active material contained in the slurry is notparticularly limited and a suitable material can be selected accordingto the type of an electrical storage device of interest.

The electrochemically active material may comprise a material for use asan active material for a positive electrode. The electrochemicallyactive material may comprise a material capable of incorporating lithium(including incorporation through lithium intercalation/deintercalation),a material capable of lithium conversion, or combinations thereof.Non-limiting examples of electrochemically active materials capable ofincorporating lithium include LiCoO₂, LiNiO₂, LiFePO₄, LiCoPO₄, LiMnO₂,LiMn₂O₄, Li(NiMnCo)O₂, Li(NiCoAl)O₂, carbon-coated LiFePO₄, andcombinations thereof. Non-limiting examples of materials capable oflithium conversion include sulfur, LiO₂, FeF₂ and FeF₃, Si, aluminum,tin, SnCo, Fe₃O₄, and combinations thereof.

The electrochemically active material may comprise a material for use asan active material for a negative electrode. The electrochemicallyactive material may comprise graphite, lithium titanate, siliconcompounds, tin, tin compounds, sulfur, sulfur compounds, or acombination thereof.

The electrochemically active material may be present in the slurry inamounts of 45% to 95% by weight, such as 70% to 98% by weight, based onthe total solids weight of the slurry.

The slurry composition of the present invention may optionally furthercomprise an electrically conductive agent. Non-limiting examples ofelectrically conductive agents include carbonaceous materials such as,activated carbon, carbon black such as acetylene black and furnaceblack, graphite, graphene, carbon nanotubes, carbon fibers, fullerene,and combinations thereof. The electrically conductive material may alsocomprise any active carbon that has a high-surface area, such as a BETsurface area of greater than 100 m²/g. As used herein, the term “BETsurface area” refers to a specific surface area determined by nitrogenadsorption according to the ASTM D 3663-78 standard based on theBrunauer-Emmett-Teller method described in the periodical “The Journalof the American Chemical Society”, 60, 309 (1938). In some examples, theconductive carbon can have a BET surface area of 100 m²/g to 1,000 m²/g,such as 150 m²/g to 600 m²/g, such as 100 m²/g to 400 m²/g, such as 200m²/g to 400 m²/g. In some examples, the conductive carbon can have a BETsurface area of about 200 m²/g. A suitable conductive carbon material isLITX 200 commercially available from Cabot Corporation. The conductivecarbon material can be present in the slurry in amounts of 2 to 20,typically 5 to 10 percent by weight based on total solids weight of theslurry.

The electrically conductive agent may be present in the slurry inamounts of 1% to 20% by weight, such as 5% to 10% by weight, based onthe total solids weight of the slurry.

The slurry composition may be in the form of an electrode slurrycomposition comprising the binder, electrochemically active material andelectrically conductive material, each as described above. The electrodeslurry may comprise such materials present in the slurry composition inthe amounts described above. For example, the electrode slurrycomposition may comprise the electrochemically active material presentin amounts of 45% to 95% by weight, such as 70% to 98% by weight; thebinder present in amounts of 1% to 20% by weight, such as 1% to 10% byweight, such as 5% to 10% percent by weight; and the electricallyconductive agent present in amounts of 1% to 20% by weight, such as 5%to 10% by weight, the percentages by weight based on the total solidsweight of the electrode slurry composition.

The electrode slurry composition comprising the organic medium,electrochemically active material, electrically conductive material,binder dispersion (which may include a separately added crosslinkingagent), additional organic medium, if needed, and optional ingredients,may be prepared by combining the ingredients to form the slurry. Thesesubstances can be mixed together by agitation with a known means such asa stirrer, bead mill or high-pressure homogenizer.

As for mixing and agitation for the manufacture of the electrode slurrycomposition, a mixer capable of stirring these components to such anextent that satisfactory dispersion conditions are met should beselected. The degree of dispersion can be measured with a particle gaugeand mixing and dispersion are preferably carried out to ensure thatagglomerates of 100 microns or more are not present. Examples of themixers which meets this condition include ball mill, sand mill, pigmentdisperser, grinding machine, extruder, rotor stator, pug mill,ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, andcombinations thereof.

The slurry composition may have a solids content of at least 30% byweight, such as at least 40% by weight, such as at least 50% by weight,such as at least 55%, such as at least 60%, such as at least 65%, suchas at least 71%, such as at least 75%, and may be no more than 90% byweight, such as no more than 85% by weight, such as no more than 75% byweight, the % by weight based on the total weight of the slurrycomposition. The slurry composition may have a solids content of 30% to90% by weight, such as 40% to 85% by weight, such as 50% to 85% byweight, such as 55% to 85% by weight, such as 60% to 85% by weight, suchas 65% to 85% by weight, such as 71% to 85% by weight, such as 75% to85% by weight, based on the total weight of the slurry composition.

The use of the organic medium and binder of the present invention mayresult in a more stable slurry composition than those previouslyemployed. For example, the slurry composition may maintain shelf-lifestability for a longer period of time than previous slurry compositionsthat used N-methyl pyrrolidone (NMP). The improved shelf-life stabilitymay be determined by measuring the viscosity of the slurry compositionperiodically over a period of time. For example, equivalent slurrycompositions may be prepared with one using the organic medium of thepresent invention and a second using NMP. The slurry compositions mayhave an initial viscosity measurement and then may be stored in sealedcontainers with a viscosity measurement taken on the 3^(rd), 10^(th) and14^(th) day of storage. As demonstrated in the examples below, theslurry composition of the present invention maintains a viscosity withinthe target range and decreases a little less than 1,500 cp over thecourse of 14 days. In contrast, the slurry composition made using NMP isgelled and unusable by the 3^(rd) day of storage. Accordingly, theslurry composition of the present invention possesses significantstorage stability over previous NMP-based slurry compositions.

The present invention is also directed to an electrode comprising anelectrical current collector and a film formed on the electrical currentcollector, wherein the film is deposited from the electrode slurrycomposition described above. The electrode may be a positive electrodeor a negative electrode and may be manufactured by applying theabove-described slurry composition to the surface of the currentcollector to form a coating film, and subsequently drying and/or curingthe coating film. The coating film may have a thickness of at least 1micron, such as 1 to 500 microns (μm), such as 1 to 150 μm, such as 25to 150 μm, such as 30 to 125 μm. The coating film may comprise across-linked coating. The current collector may comprise a conductivematerial, and the conductive material may comprise a metal such as iron,copper, aluminum, nickel, and alloys thereof, as well as stainlesssteel. For example, the current collector may comprise aluminum orcopper in the form of a mesh, sheet or foil. Although the shape andthickness of the current collector are not particularly limited, thecurrent collector may have a thickness of about 0.001 to 0.5 mm, such asa mesh, sheet or foil having a thickness of about 0.001 to 0.5 mm.

In addition, the current collector may be pretreated with a pretreatmentcomposition prior to depositing the slurry composition. As used herein,the term “pretreatment composition” refers to a composition that uponcontact with the current collector, reacts with and chemically altersthe current collector surface and binds to it to form a protectivelayer. The pretreatment composition may be a pretreatment compositioncomprising a group IIIB and/or IVB metal. As used herein, the term“group IIIB and/or IVB metal” refers to an element that is in group IIIBor group IVB of the CAS Periodic Table of the Elements as is shown, forexample, in the Handbook of Chemistry and Physics, 63^(rd) edition(1983). Where applicable, the metal themselves may be used, however, agroup IIIB and/or IVB metal compound may also be used. As used herein,the term “group IIIB and/or IVB metal compound” refers to compounds thatinclude at least one element that is in group IIIB or group IVB of theCAS Periodic Table of the Elements. Suitable pretreatment compositionsand methods for pretreating the current collector are described in U.S.Pat. No. 9,273,399 at col. 4, line 60 to col. 10, line 26, the citedportion of which is incorporated herein by reference. The pretreatmentcomposition may be used to treat current collectors used to producepositive electrodes or negative electrodes.

The method of applying the slurry composition to the current collectoris not particularly limited. The slurry composition may be applied bydoctor blade coating, dip coating, reverse roll coating, direct rollcoating, gravure coating, extrusion coating, immersion or brushing.Although the application quantity of the slurry composition is notparticularly limited, the thickness of the coating formed after theorganic medium is removed may be 25 to 150 microns (μm), such as 30 to125 μm.

Drying and/or crosslinking the coating film after application, ifapplicable, can be done, for example, by heating at elevatedtemperature, such as at least 50° C., such as at least 60° C., such as50-145° C., such as 60-120° C., such as 65-110° C. The time of heatingwill depend somewhat on the temperature. Generally, higher temperaturesrequire less time for curing. Typically, curing times are for at least 5minutes, such as 5 to 60 minutes. The temperature and time should besufficient such that the dispersant in the cured film is crosslinked (ifapplicable), that is, covalent bonds are formed between co-reactivegroups on the dispersant polymer chain, such as carboxylic acid groupsand hydroxyl groups and the N-methylol and/or the N-methylol ethergroups of an aminoplast, isocyanato groups of a blocked polyisocyanatecrosslinking agent, or in the case of a self-curing dispersant, theN-alkoxymethyl amide groups or blocked isocyanato groups. The extent ofcure or crosslinking may be measured as resistance to solvents such asmethyl ethyl ketone (MEK). The test is performed as described in ASTMD-540293. The number of double rubs, one back and forth motion, isreported. This test is often referred to as “MEK Resistance”.Accordingly, the dispersant and crosslinking agent (inclusive ofself-curing dispersants and dispersants with separately addedcrosslinking agents) is isolated from the binder composition, depositedas a film and heated for the temperature and time that the binder filmis heated. The film is then measured for MEK Resistance with the numberof double rubs reported. Accordingly, a crosslinked dispersant will havean MEK Resistance of at least 50 double rubs, such as at least 75 doublerubs. Also, the crosslinked dispersant may be substantially solventresistant to the solvents of the electrolyte mentioned below. Othermethods of drying the coating film include ambient temperature drying,microwave drying and infrared drying, and other methods of curing thecoating film include e-beam curing and UV curing.

During discharge of a lithium ion electrical storage device, lithiumions may be released from the negative electrode and carry the currentto the positive electrode. This process may include the process known asdeintercalation. During charging, the lithium ions migrate from theelectrochemically active material in the positive electrode to thenegative electrode where they become embedded in the electrochemicallyactive material present in the negative electrode. This process mayinclude the process known as intercalation.

The present invention is also directed to an electrical storage device.An electrical storage device according to the present invention can bemanufactured by using the above electrodes prepared from the electrodeslurry composition of the present invention. The electrical storagedevice comprises an electrode, a counter electrode and an electrolyte.The electrode, counter-electrode or both may comprise the electrode ofthe present invention, as long as one electrode is a positive electrodeand one electrode is a negative electrode. Electrical storage devicesaccording to the present invention include a cell, a battery, a batterypack, a secondary battery, a capacitor, and a supercapacitor.

The electrical storage device includes an electrolytic solution and canbe manufactured by using parts such as a separator in accordance with acommonly used method. As a more specific manufacturing method, anegative electrode and a positive electrode are assembled together witha separator there between, the resulting assembly is rolled or bent inaccordance with the shape of a battery and put into a battery container,an electrolytic solution is injected into the battery container, and thebattery container is sealed up. The shape of the battery may be like acoin, button or sheet, cylindrical, square or flat.

The electrolytic solution may be liquid or gel, and an electrolyticsolution which can serve effectively as a battery may be selected fromamong known electrolytic solutions which are used in electrical storagedevices in accordance with the types of a negative electrode activematerial and a positive electrode active material. The electrolyticsolution may be a solution containing an electrolyte dissolved in asuitable solvent. The electrolyte may be conventionally known lithiumsalt for lithium ion secondary batteries. Examples of the lithium saltinclude LiClO₄, LiBF₄, LiPF₆, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiBioClio,LiAlCl₄, LiCl, LiBr, LiB(C₂H₅)₄, LiB(C₆H₅)₄, LiCF₃SO₃, LiCH₃SO₃,LiC₄F₉SO₃, Li(CF₃SO₂)₂N, LiB₄CH₃SO₃Li and CF₃SO₃Li. The solvent fordissolving the above electrolyte is not particularly limited andexamples thereof include carbonate compounds such as propylenecarbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate,methyl ethyl carbonate and diethyl carbonate; lactone compounds such asγ-butyl lactone; ether compounds such as trimethoxymethane,1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and2-methyltetrahydrofuran; and sulfoxide compounds such as dimethylsulfoxide. The concentration of the electrolyte in the electrolyticsolution may be 0.5 to 3.0 mole/L, such as 0.7 to 2.0 mole/L.

As used herein, the term “polymer” refers broadly to oligomers and bothhomopolymers and copolymers. The term “resin” is used interchangeablywith “polymer”.

The terms “acrylic” and “acrylate” are used interchangeably (unless todo so would alter the intended meaning) and include acrylic acids,anhydrides, and derivatives thereof, such as their C₁-C₅ alkyl esters,lower alkyl-substituted acrylic acids, e.g., C₁-C₂ substituted acrylicacids, such as methacrylic acid, 2-ethylacrylic acid, etc., and theirC₁-C₄ alkyl esters, unless clearly indicated otherwise. The terms“(meth)acrylic” or “(meth)acrylate” are intended to cover both theacrylic/acrylate and methacrylic/methacrylate forms of the indicatedmaterial, e.g., a (meth)acrylate monomer. The term “(meth)acrylicpolymer” refers to polymers prepared from one or more (meth)acrylicmonomers.

As used herein molecular weights are determined by gel permeationchromatography using a polystyrene standard. Unless otherwise indicatedmolecular weights are on a weight average basis. As used herein, theterm “weight average molecular weight” or “(M_(w))” means the weightaverage molecular weight (M_(w)) as determined by gel permeationchromatography (GPC) using Waters 2695 separation module with a Waters410 differential refractometer (RI detector), linear polystyrenestandards having molecular weights of from 580 Da to 365,000 Da,dimethylformamide (DMF) with 0.05M lithium bromide (LiBr) as the eluentat a flow rate of 0.5 mL/min, and one Shodex Asahipak GF-510 HQ column(300×7.5 mm, 5 μm) for separation.

The term “glass transition temperature” as used herein is a theoreticalvalue, being the glass transition temperature as calculated by themethod of Fox on the basis of monomer composition of the monomer chargeaccording to T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) andJ. Brandrup, E. H. Immergut, Polymer Handbook 3^(rd) edition, JohnWiley, New York, 1989.

As used herein, unless otherwise defined, the term substantially freemeans that the component is present, if at all, in an amount of lessthan 5% by weight, based on the total weight of the slurry composition.

As used herein, unless otherwise defined, the term essentially freemeans that the component is present, if at all, in an amount of lessthan 1% by weight, based on the total weight of the slurry composition.

As used herein, unless otherwise defined, the term completely free meansthat the component is not present in the slurry composition, i.e., 0.00%by weight, based on the total weight of the slurry composition.

As used herein, the term “total solids” refers to the non-volatilecomponents of the slurry composition of the present invention andspecifically excludes the organic medium.

As used herein, the term “consists essentially of” includes the recitedmaterial or steps and those that do not materially affect the basic andnovel characteristics of the claimed invention.

As used herein, the term “consists of” excludes any element, step oringredient not recited.

For purposes of the detailed description, it is to be understood thatthe invention may assume various alternative variations and stepsequences, except where expressly specified to the contrary. Moreover,other than in any operating examples, or where otherwise indicated, allnumbers such as those expressing values, amounts, percentages, ranges,subranges and fractions may be read as if prefaced by the word “about,”even if the term does not expressly appear. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties to be obtained by the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques. Where a closed or open-ended numerical range is describedherein, all numbers, values, amounts, percentages, subranges andfractions within or encompassed by the numerical range are to beconsidered as being specifically included in and belonging to theoriginal disclosure of this application as if these numbers, values,amounts, percentages, subranges and fractions had been explicitlywritten out in their entirety.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard variation found in theirrespective testing measurements.

As used herein, unless indicated otherwise, a plural term can encompassits singular counterpart and vice versa, unless indicated otherwise. Forexample, although reference is made herein to “an” electrochemicallyactive material, “a” fluoropolymer, “a” dispersant, and “an”electrically conductive agent, a combination (i.e., a plurality) ofthese components can be used. In addition, in this application, the useof “or” means “and/or” unless specifically stated otherwise, even though“and/or” may be explicitly used in certain instances.

As used herein, “including,” “containing” and like terms are understoodin the context of this application to be synonymous with “comprising”and are therefore open-ended and do not exclude the presence ofadditional undescribed or unrecited elements, materials, ingredients ormethod steps. As used herein, “consisting of” is understood in thecontext of this application to exclude the presence of any unspecifiedelement, ingredient or method step. As used herein, “consistingessentially of” is understood in the context of this application toinclude the specified elements, materials, ingredients or method steps“and those that do not materially affect the basic and novelcharacteristic(s)” of what is being described. Although variousembodiments of the invention have been described in terms of“comprising”, embodiments consisting essentially of or consisting of arealso within the scope of the present invention.

As used herein, the terms “on,” “onto,” “applied on,” “applied onto,”“formed on,” “deposited on,” “deposited onto,” mean formed, overlaid,deposited, or provided on but not necessarily in contact with thesurface. For example, a composition “deposited onto” a substrate doesnot preclude the presence of one or more other intervening coatinglayers of the same or different composition located between theelectrodepositable coating composition and the substrate.

Whereas specific embodiments of the invention have been described indetail, it will be appreciated by those skilled in the art that variousmodifications and alternatives to those details could be developed inlight of the overall teachings of the disclosure. Accordingly, theparticular arrangements disclosed are meant to be illustrative only andnot limiting as to the scope of the invention which is to be given thefull breadth of the claims appended and any and all equivalents thereof.

Aspects

Each of the characteristics and examples described above, andcombinations thereof, may be said to be encompassed by the presentinvention. The present invention is thus drawn in particular, withoutbeing limited thereto, to the following aspects:

1. A slurry composition comprising:

(a) a binder comprising a polymer comprising a fluoropolymer dispersedin an organic medium; and at least one of

(b1) an electrochemically active material, and

(b2) an electrically conductive agent,

wherein the organic medium has an evaporation rate less than 10 g/minm², at the dissolution temperature of the fluoropolymer in the organicmedium.

2. The slurry composition of Aspect 1, wherein the electrochemicallyactive material comprises a material capable of incorporating lithium.

3. The slurry composition of Aspect 2, wherein material capable ofincorporating lithium comprises LiCoO₂, LiNiO₂, LiFePO₄, LiCoPO₄,LiMnO₂, LiMn₂O₄, Li(NiMnCo)O₂, Li(NiCoAl)O₂, carbon-coated LiFePO₄, or acombination thereof.

4. The slurry composition of Aspect 1, wherein the electrochemicallyactive material comprises a material capable of lithium conversion.

5. The slurry composition of Aspect 4, wherein the material capable oflithium conversion comprises sulfur, LiO₂, FeF₂ and FeF₃, Si, aluminum,tin, SnCo, Fe₃O₄, or combinations thereof.

6. The slurry composition of Aspect 1, wherein the electrochemicallyactive material comprises graphite, silicon compounds, tin, tincompounds, sulfur, sulfur compounds, or a combination thereof 7. Theslurry composition of any one of Aspects 1 to 6, wherein thefluoropolymer comprises a (co)polymer comprising the residue ofvinylidene fluoride.

8. The slurry composition of Aspect 7, wherein the fluoropolymercomprises a polyvinylidene fluoride homopolymer.

9. The slurry composition of any one of Aspects 1 to 8, furthercomprising a dispersant.

10. The slurry composition of Aspect 9, wherein the dispersant comprisesan addition polymer.

11. The slurry composition of Aspect 10, wherein the addition polymerhas a glass transition temperature less than 100° C.

12. The slurry composition of Aspect 11, wherein the addition polymerhas a glass transition temperature of −50° C. to +70° C.

13. The slurry composition of any one of Aspects 10 to 12, wherein theaddition polymer comprises an active hydrogen group.

14. The slurry composition of Aspect 13, wherein the active hydrogengroup comprises at least one carboxylic acid group.

15. The slurry composition of Aspects 13 or 14, wherein the activehydrogen group comprises at least one hydroxyl group.

16. The slurry composition of any one of Aspects 10 to 15, wherein theaddition polymer comprises a (meth)acrylic polymer comprisingconstitutional units comprising the residue of methyl methacrylate.

17. The slurry composition of any one of Aspects 10 to 16, wherein theaddition polymer comprises a (meth)acrylic polymer comprisingconstitutional units comprising the residue of 2-ethylhexyl acrylate.

18. The slurry composition of Aspects 16 or 17, wherein the(meth)acrylic polymer further comprises constitutional units comprisingthe residue of ethylenically unsaturated monomer comprising aheterocyclic group.

19. The slurry composition of any one of Aspects 16 to 18, wherein the(meth)acrylic polymer further comprises at least one epoxy functionalgroup, and the epoxy functional group is post-reacted with abeta-hydroxy functional acid.

20. The slurry composition of any one of Aspects 16 to 19, wherein the(meth)acrylic polymer is prepared by conventional free radical initiatedsolution polymerization of a mixture of ethylenically unsaturatedmonomers dissolved in a second organic medium.

21. The slurry composition of Aspect 20, wherein the second organicmedium used to prepare the (meth)acrylic polymer is the same as theorganic medium of the slurry composition.

22. The slurry composition of Aspects 20 or 21, wherein the secondorganic medium comprises triethylphosphate.

23. The slurry composition of any one of Aspects 9 to 22, referring backto 9, wherein the fluoropolymer and the dispersant are not bound by acovalent bond.

24. The slurry composition of any one of Aspects 9 to 23, referring backto 9, wherein the composition further comprises a cross-linker.

25. The slurry composition of any one of Aspects 9 to 23, referring backto 9, wherein the dispersant is self-crosslinking.

26. The slurry composition of any one of Aspects 1 to 25, wherein theorganic medium has an evaporation rate greater than 80 g/min m², at 180°C.

27. The slurry composition of any one of Aspects 1 to 26, wherein theorganic medium comprises butyl pyrrolidone, trialkyl phosphate such astriethylphosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5,4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, dimethylphthalate, methyl isoamyl ketone, ethyl propionate, 1-ethoxy-2-propanol,dipropylene glycol dimethyl ether, saturated and unsaturated linear andcyclic ketones, diisobutyl ketone, acetate esters, tripropylene glycolmethyl ether, diethylene glycol ethyl ether acetate, or combinationsthereof.

28. The slurry composition of any one of Aspects 1 to 27, wherein theorganic medium comprises a primary solvent and a co-solvent, the primarysolvent comprising butyl pyrrolidone, a trialkylphosphate such astriethylphosphate, 3-methoxy-N,N-dimethylpropanamide,1,2,3-triacetoxypropane, or combinations thereof, and the co-solventcomprising ethyl acetoacetate, gamma-butyrolactone, propylene glycolmethyl ether, dipropylene glycol methyl ether, propylene glycolmonopropyl ether, diethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, or combinations thereof.

29. The slurry composition of Aspect 28, wherein the primary solvent ispresent in an amount of 50% to 99% by weight, such as 65% to 90% byweight, such as 75% to 85% by weight, and the co-solvent is present inan amount of 1% to 50% by weight, such as 10% to 35% by weight, such as15% to 25% by weight, each based on the total weight of the organicmedium.

30. The slurry composition of any of one of Aspects 27 to 29, where theorganic medium comprises triethyl phosphate or essentially consists oftriethyl phosphate.

31. The slurry composition of Aspects 28 or 29, wherein the organicmedium comprises triethyl phosphate as the primary solvent and ethylacetoacetate as a co-solvent.

32. The slurry composition of any one of Aspects 1 to 31, comprisingboth (b1) the electrochemically active material and (b2) theelectrically conductive agent.

33. The slurry composition of any one of Aspects 1 to 32, wherein theelectrically conductive agent comprises activated carbon, carbon blacksuch as acetylene black and furnace black, graphite, graphene, carbonnanotubes, carbon fibers, fullerene, or combinations thereof.

34. The slurry composition of any one of Aspects 1 to 33, wherein theelectrically conductive agent comprises conductive carbon materialhaving a surface area of 100 m²/g to 1000 m²/g.

35. The slurry composition of any one of Aspects 32 to 34, wherein theelectrochemically active material (b1) is present in amounts of 70 to 99percent by weight; the binder (a) is present in amounts of 0.5 to 20percent by weight and the electrically conductive agent (b2) is presentin amounts of 0.5 to 20 percent by weight, based on the total weight ofsolids in the slurry.

36. The slurry composition of any one of Aspects 1 to 35, furthercomprising an adhesion promoter.

37. The slurry composition of any one of Aspects 1 to 36, wherein theslurry is substantially free of isophorone.

38 The slurry composition of any one of Aspects 1 to 37, which comprises0 to less than 5% by weight of N-methyl-2-pyrrolidone, based on thetotal weight of the slurry composition.

39. The slurry composition of Aspect 38, wherein the slurry issubstantially free of N-methyl-2-pyrrolidone.

40. The slurry composition of any of the preceding Aspects, wherein thebinder solids are present in the slurry composition in amounts of 1% to20% by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry, based on thetotal solids weight of the slurry.

41. The slurry composition of Aspect 9, wherein the binder solids arepresent in the slurry composition in amounts of 1% to 20% by weight,such as 1% to 10% by weight, such as 5% to 10% percent by weight, basedon the total solids weight of the slurry, based on the total solidsweight of the slurry, and the fluoropolymer is present in the binder inamounts of 40% to 96% by weight, such as 50% to 90% by weight; and thedispersant is present in amounts of 2% to 20% by weight, such as 5% to15% by weight, the % by weight being based on the total weight of thebinder solids.

42. The slurry composition of Aspect 24, wherein the binder solids arepresent in the slurry composition in amounts of 1% to 20% by weight,such as 1% to 10% by weight, such as 5% to 10% percent by weight, basedon the total solids weight of the slurry, and the fluoropolymer ispresent in the binder in amounts of 40% to 96% by weight, such as 50% to90% by weight; the dispersant is present in amounts of 2% to 20% byweight, such as 5% to 15% by weigh; and the separately added crosslinkermay be present in amounts of up to 15% by weight, such as 1% to 15% byweight, the % by weight being based on the total weight of the bindersolids.

43. The slurry composition of Aspect 36, wherein the binder solids arepresent in the slurry composition in amounts of 1% to 20% by weight,such as 1% to 10% by weight, such as 5% to 10% percent by weight, basedon the total solids weight of the slurry, and the fluoropolymer ispresent in the binder in amounts of 40% to 96% by weight, such as 50% to90% by weight; the dispersant is present in amounts of 2% to 20% byweight, such as 5% to 15% by weight; and the adhesion promoter ispresent in the slurry composition in an amount of 10% to 60% by weight,20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50%by weight, such as 15% to 40% by weight, such as 20% to 30% by weight,such as 35% to 35% by weight, the % by weight being based on the totalweight of the binder solids.

44. The slurry composition of Aspect 36, wherein the binder solids arepresent in the slurry composition in amounts of 1% to 20% by weight,such as 1% to 10% by weight, such as 5% to 10% percent by weight, basedon the total solids weight of the slurry, and the fluoropolymer ispresent in the binder in amounts of 40% to 96% by weight, such as 50% to90% by weight; the dispersant is present in amounts of 2% to 20% byweight, such as 5% to 15% by weight; the adhesion promoter is present inthe slurry composition in an amount of 10% to 60% by weight, 20% to 60%by weight, such as 30% to 60% by weight, such as 10% to 50% by weight,such as 15% to 40% by weight, such as 20% to 30% by weight, such as 35%to 35% by weight; and the separately added crosslinker may be present inamounts of up to 15% by weight, such as 1% to 15% by weight, the % byweight being based on the total weight of the binder solids.

45. The slurry composition of any of the preceding Aspects, wherein theelectrochemically active material is present in the slurry compositionin amounts of 45% to 95% by weight, such as 70% to 98% by weight, basedon the total solids weight of the slurry.

46. The slurry composition of any of the preceding Aspects, wherein theelectrically conductive agent is present in the slurry composition inamounts of 1% to 20% by weight, such as 5% to 10% by weight, based onthe total solids weight of the slurry.

47. An electrode comprising:

-   -   (a) an electrical current collector; and    -   (b) a film formed on the electrical current collector, wherein        the film is deposited from the slurry composition of any one of        Aspect 32 to 35 or 36 to 39 referring back to aspect 32.

48. The electrode of Aspect 47, wherein the electrical current collector(a) comprises copper or aluminum in the form of a mesh, sheet or foil.

49. The electrode of Aspects 47 or 48, wherein the electrode comprises apositive electrode.

50. The electrode of Aspects 47 or 48, wherein the electrode comprises anegative electrode.

51. The electrode of any one of Aspects 47 to 50, wherein the film iscross-linked.

52. The electrode of any one of Aspects 47 to 51, wherein the electricalcurrent collector is pretreated with a pretreatment composition.

Illustrating the invention are the following examples, which, however,are not to be considered as limiting the invention to their details.Unless otherwise indicated, all parts and percentages in the followingexamples, as well as throughout the specification, are by weight.

EXAMPLES Example 1. Preparation of a Dispersant Composition

List of synthesis charge components with amounts added:

Amount Ingredients (gram) Charge 1: methylether of propylene glycol658.0 Charge 2: methyl methacrylate 784.8 (premixed) ethyl acrylate435.9 2-ethylhexyl acrylate 336.3 hydroxyl ethyl acrylate 33.2methacrylic acid 33.15 Charge 3: Tertiary amyl peroxy 2-ethyl hexylcarbonate 33.8 (premixed) methylether of propylene glycol 169.6 Charge4: Tertiary amyl peroxy 2-ethyl hexyl carbonate 11.9 (premixed)methylether of propylene glycol 169.6 Charge 5: methylether of propyleneglycol 584.6

To a suitable reaction vessel equipped with a stirrer, reflux condenser,thermometer, heating mantle and nitrogen inlet, charge 1 was added atambient temperature. The temperature was then increased to reflux (˜120°C.), at which temperature the monomer premix of charge 3 was added over185 minutes. Five minutes after the start of the addition of charge 3,charge 2 was added over 180 minutes. Upon completion of the addition ofcharges 2 and 3, charge 4 was added over 60 minutes, followed by a holdfor additional 60 minutes at reflux (˜120° C.). Thereafter the reactionmixture was cooled to 40° C. and charge 5 was added with a subsequent30-minute hold period. The dispersant composition thus formed had atheoretical (calculated) solids content of 51% by weight. The dispersanthad a theoretical glass transition temperature (Tg) of −12° C.

Solids contents of dispersant compositions were measured in eachdispersant example by the following procedure. An aluminum weighing dishfrom Fisher Scientific, was weighed using an analytical balance. Theweight of the empty dish was recorded to four decimal places.Approximately 0.5 g of dispersant and 3.5 g of acetone was added to theweigh dish. The weight of the dish and the dispersant solution wasrecorded to four decimal places. The dish containing the dispersantsolution was placed into a laboratory oven, with the oven temperatureset to 110 degrees centigrade, and dried for 1 hour. The dish and drieddispersant was weighed using an analytical balance. The weight of thedish and dried dispersant was recorded to four decimal places. Thesolids was determined using the following equation: %solids=100×[(weight of the dish and the dry dispersant)−(weight of theempty dish)]/[(weight of the dish and the dispersant solution)−(weightof the empty dish)].

Example 2. Preparation of Binder Dispersion

In a plastic container was placed 199.5 grams of Tamisolve NxG (organicsolvent, available from Eastman Chemical CO.) and 82.1 grams of thedispersant composition from Example 1. The resulting mixture was stirredvigorously using a Cowles blade. This mixing was continued while 118.4grams of polyvinylidene difluoride powder (PVDF T-1, available fromInner Mongolia 3F Wanhao Fluorochemical Co., Ltd) was added gradually.Mixing was continued for an additional 20 minutes after all thepolyvinylidene difluoride powder was added. This dispersion had a volumeweighted mean particle size of 976 nm as determined by dynamic lightscattering method.

Example 3. Preparation of Binder Dispersion with Crosslinking Agent

To a plastic container was added 1.05 grams Cymel 303 (melaminecrosslinking agent, available from CYTEC) and 50.0 grams of thefluoropolymer dispersion from Example 2. This mixture was agitated witha dual asymmetric mixer at 2000 RPM for 5 minutes.

Example 4. Preparation of Slurry Composition and Electrode

To a plastic cup was added Tamisolve NxG (22.25 grams), and the binderdispersion from Example 3 (3.48 grams). An electrically conductive agent(LITX200, conductive carbon available from Cabot, 1.07 grams) was addedin two portions with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes. Cathode active powderNMC-111 (33.20 grams, electrochemically active material (Li(NiMnCo)O₂),available from BASF) was added in two portions to this mixed blend, witheach sequential blend mixed in a dual-asymmetric centrifugal mixer at2000 rpm for 5 minutes to produce the formulated slurry. The totalnon-volatiles content of this slurry was 59.5 weight %. The final ratioof NMC-111:LITX200:Binder dry solids was 93:3:4.

Solids contents for all compositions other than the dispersantcompositions were measured by the following procedure. An aluminumweighing dish from Fisher Scientific, was weighed using an analyticalbalance. The weight of the empty dish was recorded to four decimalplaces. Approximately 1 g of dispersion was added to the weighed dish.The weight of the dish and the wet dispersion was recorded to fourdecimal places. The dish containing the slurry was placed into alaboratory oven, with the oven temperature set to 120° C. and dried for1 hour. The dish and dried dispersion was weighed using an analyticalbalance. The weight of the dish and dried slurry was recorded to fourdecimal places. The solids was determined using the following equation:% solids=100×[(weight of the dish and the dry dispersion)−(weight of theempty dish)]/[(weight of the dish and the wet dispersion)−(weight of theempty dish)].

An electrode was prepared by depositing a wet film on a pre-cleanedaluminum foil by a draw-down application of the slurry composition usinga doctor blade. This wet film was heated in an oven to a maximumtemperature of 110° C. for at least 10 minutes. After cooling, anaverage dry film thickness of 76 microns was determined from fivemeasurements with a micrometer. The dry film was pressed in apinch-roller calender press (available from Innovative Machine Co.) to afilm thickness of 56 microns. The resultant film's adhesion peelstrength was tested according to the PEEL STRENGTH TEST METHOD, and thecoating demonstrated a 90-degree peel strength of 15.5 N/m.

The battery performance of an electrode having a coating prepared usingthe same method with a pressed-film thickness of 47 microns, is shown inTable 1.

TABLE 1 Battery Performance of coatings from Example 4: % CapacityRetention Discharge C-Rate (hour⁻¹) after about 50 cycles ExampleTemperature 0.2 0.4 0.8 1.0 1.6 3.2 6.4 at C-rate of 1.0 4 25° C. 133.2126.2 113.8 107.7 91.2 25.7 0 97.7 Table shows cell specific capacity(milliamp-hours per gram) for various discharge C-rates (per hour).

Example 5. Preparation of a Dispersant Composition

Amount Ingredients (gram) Charge 1: Triethylphosphate 375.4 Charge 2:Triethylphosphate 61.1 (premixed) Tertiary amyl peroxy 2-ethyl hexylcarbonate 12.9 Charge 3: methyl methacrylate 228.2 (premixed) ethylacrylate 91.6 methacrylic acid 0 hydroxyethyl acrylate 11.5 ethylhexylacrylate 193.8 glycidyl methacrylate 58.4 Charge 4: Triethylphosphate21.99 Charge 5: Tertiary amyl peroxy 2-ethyl hexyl carbonate 4.3(premixed) Triethylphosphate 61.17 Charge 6: Triethylphosphate 57.9

To a suitable reaction vessel equipped with a stirrer, condenser,thermometer, heating mantle and nitrogen inlet, Charge 1 was added atambient temperature. The temperature was then increased to 120° C., atwhich temperature the initiator premix of Charge 2 was added over 185minutes. Five minutes after the start of the addition of Charge 2,Charge 3 was added over 180 minutes. Upon completion of the addition ofCharges 2 and 3, Charge 4 was added, followed by Charge 5 added over 60minutes, followed by addition of Charge 6 and an additional 60-minutehold at 120° C. After cooling to below 90° C., the dispersantcomposition thus formed had a theoretical solids content of 51.32 weight%. The dispersant had a theoretical glass transition temperature (Tg) of−12.4° C.

Example 6. Preparation of a Dispersant Composition

This dispersant composition was prepared the same way as the dispersantcomposition of Example 5, except Charge 3 consisted of the followingmonomers and the dispersant had a theoretical glass transitiontemperature (Tg) of −12.2° C.:

Charge 3: methyl methacrylate 228.2 (premixed) ethyl acrylate 58.4methacrylic acid 11.5 Hydroxyethyl acrylate 11.5 Ethylhexyl acrylate215.7 Vinyl Pyrrolidone 58.4

Examples 7 and 8. Preparation of Binder Dispersions

In a 2-liter plastic container, was placed 41.64 grams oftriethylphosphate, 26.85 grams of the dispersant composition from eitherExample 5 or 6 as noted below. The resultant mixture was stirredvigorously using a Cowles blade while maintaining a modest vortex. Thismixing was continued while 32.90 grams of polyvinylidene difluoridepowder, PVDF T-1 (available from Inner Mongolia 3F Wanhao FluorochemicalCo., Ltd) was added in small portions. Mixing was continued for anadditional 30 minutes after all the polyvinylidene difluoride powder wasadded. As shown in the table below, PVDF dispersions were prepared fromcombinations of (meth)acrylic copolymer and PVDF at the specified weightratios.

PVDF Dispersant weight, weight, Binder percent percent of DispersionDispersant Polyvinylidene of dry solid dry solid Example from:Difluoride components components Example 7 Example 5 PVDF T-1 70.9 29.1Example 8 Example 6 PVDF T-1 69.7 30.3

Example 9. Preparation of Slurry Composition

To a plastic cup was added triethylphosphate (14.83 grams), and thebinder dispersion from Example 8 (2.15 grams). Conductive carbon LITX200(0.72 grams) was added in two portions with each sequential blend mixedin a dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.Cathode active powder NMC-111 (22.33 grams) was added in two portions tothis mixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce the formulatedslurry. The total non-volatiles content of this slurry was 60 weight %.The final ratio of NMC-111:LITX200:Binder dry solids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 106microns was determined from five measurements with a micrometer. The dryfilm was pressed in a pinch-roller calender press (Innovative MachineCo.) to a film thickness of 87 microns. The resultant film's adhesionpeel strength was tested according to the PEEL STRENGTH TEST METHOD, andthe coating demonstrated a 90-degree peel strength of 7.9 N/m.

Example 10. Preparation of Slurry Composition

To a plastic cup was added triethylphosphate (14.71 grams), and thebinder dispersion from Example 7 (2.27 grams). Conductive carbon LITX200(0.72 grams) was added in two portions with each sequential blend mixedin a dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.Cathode active powder NMC-111 (22.33 grams) was added in two portions tothis mixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 60%. Thefinal ratio of NMC-111:LITX200:Binder dry solids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 68° C. for atleast 10 minutes. After cooling, an average dry film thickness of 74microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 57 microns. Theresultant film's adhesion peel strength was tested according to the PEELSTRENGTH TEST METHOD, and the coating demonstrated a 90-degree peelstrength of 11.2 N/m.

Example 11. Preparation of a Dispersant Composition

A dispersant composition was prepared as follows: To a four neck roundbottom flask, 375.4 grams of triethylphosphate (TEP) was added and theflask was set up with a mechanical stir blade, thermocouple, and refluxcondenser. The flask containing TEP solvent was heated to a set point of120° C. under a nitrogen atmosphere. A monomer solution containing 228.2grams of methyl methacrylate (MMA), 215.7 grams of 2-ethylhexyl acrylate(EHA), 58.4 grams of ethyl acrylate (EA), 58.4 grams of N-vinylpyrrolidone (NVP), 11.5 grams of hydroxyethyl acrylate (HEA), and 11.5grams of methacrylic acid (MAA) was thoroughly mixed in a separatecontainer. A solution of 12.9 grams of tert-amylperoxy 2-ethylhexylcarbonate initiator (Trigonox 131, available from AkzoNobel) and 61.1grams of TEP was prepared and added into the flask over 185 minutes.Five minutes after the initiator solution started, addition of themonomer solution was started and the monomer solution was added to theflask over 180 minutes. After both initiator and monomer feeds werecomplete, the monomer addition funnel was rinsed with 14.4 grams of TEP.Then another solution of 4.3 grams of Trigonox 131 and 61.1 grams of TEPwas added over 60 minutes. After this second initiator feed wascomplete, the initiator addition funnel was rinsed with 57.9 grams ofTEP. The reaction mixture was then held at 120° C. for 60 minutes. Afterthe 60-minute hold, the reaction mixture was cooled and poured into asuitable container. The final measured solids content of the dispersantcomposition was determined to be 51.02 weight %. The dispersant had atheoretical glass transition temperature (Tg) of −12.2° C.

Example 12. Preparation of a Dispersant Composition

A dispersant composition was prepared as follows: In a four neck roundbottom flask, 375.4 grams of triethylphosphate (TEP) was added and theflask was set up with a mechanical stir blade, thermocouple, and refluxcondenser. The flask containing TEP solvent was heated to a set point of120° C. under a nitrogen atmosphere. A monomer solution containing 228.2grams of MMA, 175.3 grams of EHA, 157 grams of EA, 11.5 grams of HEA,and 11.5 grams of MAA was thoroughly mixed in a separate container. Asolution of 12.9 grams of Trigonox 131 and 61.1 grams of TEP wasprepared and added into the flask over 185 minutes. Five minutes afteraddition of the initiator solution started, addition of the monomersolution was started and continued over 180 minutes. After bothinitiator and monomer feeds were complete, the monomer addition funnelwas rinsed with 14.4 grams of TEP. Then another solution of 4.3 grams ofTrigonox 131 and 61.1 grams of TEP was added over 60 minutes. After thissecond initiator feed was complete, the initiator addition funnel wasrinsed with 57.9 grams of TEP. The reaction mixture was then held at120° C. for 60 minutes. After the 60-minute hold, the reaction mixturewas cooled and poured into a suitable container. The final measuredsolids of the dispersant composition were determined to be 50.50 weight%. The dispersant had a theoretical glass transition (Tg) of −12° C.

Example 13. Preparation of a Binder Dispersion

A binder dispersion was prepared as follows: 34.75 g of the dispersantcomposition of Example 12, 24.50 g of the dispersant composition ofExample 11, 75 g of triethylphosphate and 25 g of ethyl acetoacetatewere added to a 1,000 mL high density polyethylene container. Thehigh-density polyethylene container containing the dispersants andsolvent components was placed into a 2 L water bath and clamped toprevent movement. The dispersants and solvent components were mixedusing a 2-inch diameter Cowles mixing impeller for 5 minutes with arotation rate of 500 RPM. 100 g of polyvinylidene fluoride polymer (PVDFT-1 from Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd.) was addedgradually over 30 minutes to the dispersant solution while maintainingconstant agitation using a 2-inch diameter Cowles mixing impeller with arotation rate of 500 RPM. The components were then mixed using a 2-inchdiameter Cowles mixing impeller for 40 minutes at 1,600 RPM. Care wastaken to ensure that the slurry temperature did not rise above 40° C.During the mixing, the water in the water bath was maintained atapproximately 22-25° C. The water bath was used to prevent thenanoparticle binder dispersion from heating up during mixing. Thetemperature of nanoparticle binder dispersion was maintained below 40°C. through-out the dispersion process. The solids of the binderdispersion were determined to be 50% by weight. The resultantnanoparticle binder dispersion was a high solids and shear thinningmaterial that required brief agitation to achieve ease of handlingduring subsequent use.

Example 14. Preparation of Adhesion Promoter Composition

An adhesion promoter composition was prepared as follows: 636 g oftriethylphosphate and 33.50 g of ethyl acetoacetate were added to a2,000 mL glass container and heated to 40° C. using a hot plate. Thewarm solvent mixture was transferred to a 2,000 mL high densitypolyethylene container. The solvent components were mixed using a 2-inchdiameter Cowles mixing impeller for 5 minutes with a rotation rate of500 RPM. 35.75 g of adhesion promoter (Solef 5130 grade PVDF availablefrom Solvay) was added gradually over 30 minutes to the warm solventwhile maintaining constant agitation using a 2-inch diameter Cowlesmixing impeller with a rotation rate of 500 RPM. The components werethen mixed using a 2-inch diameter Cowles mixing impeller for 120minutes at 1600 RPM. The solids of the composition were determined to be5% by weight.

Example 15: Preparation of a Slurry Composition

A slurry composition was prepared as follows: Slurry components weremixed in a polypropylene cup held in a PTFE adaptor using a dualasymmetric centrifugal mixer Model ARM-310, made by Thinky Corporation,Japan. Before preparing the slurry, the individual binder componentsfrom Examples 11 and 12 were agitated by shaking for 30 seconds, untillow enough in viscosity to dispense. 4.524 g of the nanoparticledispersion binder of Example 11 and then 42.24 g of a solvent thinner(80:20 mix by weight of triethylphosphate and ethyl acetoacetate) wereadded to a 250 mL polypropylene mixing cup. The components were thenmixed using a dual asymmetric centrifugal mixer for 1 minute at 2000RPM. The diluted binder was clear and low viscosity. 2.81 g ofelectrically conductive agent (Timcal Super P carbon black from ImerysGraphite & Carbon Belgium SA) was added to the diluted binder. Thecomponents were then mixed using a dual asymmetric centrifugal mixer for5 minutes at 1000 RPM. Care was taken to ensure that the slurrytemperature did not rise above 40° C. After mixing, the carbon black inbinder solution was held without mixing for 5 minutes before proceedingfurther. After the above 5-minute hold period, 15 g electrochemicallyactive material (Phostech P2 Lithium Iron Phosphate (LFP) from JohnsonMatthey) was added to the carbon black and binder mix. The componentswere then mixed using a dual asymmetric centrifugal mixer for 5 minutesat 500 RPM followed by 5 minutes at 1500 RPM. Care was taken to ensurethat the slurry temperature did not rise above 40° C. A further 15 gPhostech P2 LFP was added to the mix. The components were then mixedusing a dual asymmetric centrifugal mixer for 5 minutes at 500 RPMfollowed by 5 minutes at 1500 RPM. Care was taken to ensure that theslurry temperature did not rise above 40° C. A further 11.28 g PhostechP2 LFP was added to the mix. The components were then mixed using a dualasymmetric centrifugal mixer for 5 minutes at 500 RPM followed by 5minutes at 1000 RPM. Care was taken to ensure that the slurrytemperature did not rise above 40° C. After mixing, the slurry was heldwithout mixing for 10 minutes before proceeding further. 11.165 g of theadhesion promoter composition of Example 14 was added to the mix. Thecomponents were then mixed using a dual asymmetric centrifugal mixer for5 minutes at 1000 RPM. The slurry was held without mixing for 5 minutesbefore proceeding further. The components were then mixed using a dualasymmetric centrifugal mixer for 20 minutes at 500 RPM. Care was takento ensure that the slurry temperature did not rise above 40° C. Aftermixing, the slurry was held without mixing for 10 minutes beforeproceeding further. The components were then mixed using a dualasymmetric centrifugal mixer for 20 minutes at 500 RPM followed by 5minutes at 1000 RPM. Care was taken to ensure that the slurrytemperature did not rise above 40° C.

The solids of the resultant slurry composition were determined to be 46weight %. The viscosity of the resultant slurry composition was measuredusing a Brookfield viscometer model LVDV-I+, using spindle number 3 froman LV spindle set with a rotation rate of 20 RPM. The viscosity wasmeasured immediately following mixing (day 1), two days later (day 3),nine days later (day 10) and thirteen days later (Day 14). The measuredBrookfield viscosities are shown in Table 2.

Example 16: Preparation of an Electrode

A positive electrode was prepared as follows: An approximately 6 cm by30 cm sample of 15-micron thick aluminum foil was placed onto an AFA-IIautomatic thick film coater from MTI Corporation, wiped with acetone andthen wiped with isopropanol. To the cleaned aluminum foil, an aliquot ofthe slurry composition of Example 15 was applied as a wet coating usinga 10 cm wide doctor blade with a blade gap setting of approximately 125microns.

Foils coated with wet coatings were dried using a Despatch brand Class Alaboratory box oven with a 2.5″ diameter exhaust duct and a Protocol 3programmable controller using the following ramp-and-soak conditions:Initial set point of 55° C.; place the coated foil into the oven; holdat 55° C. for 3 minutes; ramp from 55° C. to 70° C. over 1 minute; holdat 70° C. for 2 minutes; ramp from 70° C. to 90° C. over 4 minutes;remove the coated foil from the oven.

The dry film thickness (DFT) of the coating on the foil was measuredusing a digital micrometer, taking an average of six measurements, andsubtracting the thickness of uncoated foil to calculate the thickness ofthe coating only. The measured DFT is shown in Table 3.

A nine square centimeter area of coated foil was weighed using ananalytical balance. The weight of the foil and dried slurry coating wasrecorded to four decimals. A nine square centimeter area of uncoatedfoil was also weighed using an analytical balance. The weight of theuncoated foil was recorded to four decimals. The weight of the driedcoating was calculated by subtracting the weight of the uncoated foilfrom the weight of the coated foil.

The measured volume of the coating was determined by multiplying thearea of the coated foil (nine square centimeters) by the averagemeasured thickness of the coating. The porosity of the dried coated foilwas calculated based on the measured volume of the coating, the measuredmass of the coating, the composition of the coating and the knowndensities of the components. The calculated porosity of the coating ascoated is shown in Table 3.

The dried coated foils were then pressed using an IMC calender presswith 8-inch diameter rolls and a line speed of 0.2 meters per minute toa target porosity of 35%. The pressed film thickness (PFT) of thecoating calendared to 35% porosity, measured using a digital micrometer,is shown in Table 4.

The flexibility of the calender pressed films was examined using apentagon mandrel bend test apparatus and using the test method detailedin FTMS No. 141, Method 6221, Flexibility with a ⅛-inch radius mandrel.If failure is observed, using a ⅛-inch radius mandrel, an untested areais tested using a larger radius mandrel until no failure is observed,and the radius at which a pass is first observed is noted. The pentagonmandrel bend test apparatus has test radii of ⅛, ¼, ⅜, ½, ⅝, ¾ and 1inch. The results are included in Table 3.

The peel strength of the calender pressed films were determined usingthe following procedure: Firstly, samples of the pressed coated foilwere mounted. Four approximately 100 mm long pieces of 12.7 mm wide 3M™Double Coated Tape 444 were each adhered to four separate steel panelsusing one side of the double coated tape. Four strips approximately14-15 mm wide and approximately 140-160 mm in length were cut from thepressed coated foils. Each of the four strips was then adhered to theother side of the double coated tape on the steel panels, such that thecoated side of the foil was contacting the adhesive tape and also suchthat about 40-60 mm of the pressed coated foil remained free andun-adhered. One ¼ inch size binder clip was clipped to the free andun-adhered end of the pressed coated foil. Secondly, the first mountedfoil was placed, onto the sample stage of an ESM303 MotorizedTension/Compression Test Stand fitted with a Series 5 advanced digitalforce gauge, model M5-5, a model DC4060 digital control panel, and amodel G1045 90-degree peel fixture. The mounted foil was held in placemagnetically, and the binder clip was attached to the sampling fixtureof the force gauge. Thirdly, the peel strength of the pressed coatingwas measured for an average of 600 measurements with a sample rate of0.2 s and a peel rate of 50 mm per minute. The peel strength data wascollected using MESUR™ gauge software on a pc. These mounting andmeasuring steps were repeated for the remaining three strips. The datafrom the four strips were analyzed to determine an average peel strengthand a standard deviation for peel strength in N/m which are shown inTable 4. The data from the four strips were analyzed to determine anaverage peel strength and a standard deviation for peel strength in N/mwhich are shown in Table 4. The failure mode of the peeled foil was alsoassessed visually and noted as being “adhesive/clean”, or“adhesive/dirty”, or “cohesive”, or “mixed”, such that “adhesive/clean”.

Example 17: Preparation of a Comparative PVDF Binder Composition in NMP

A comparative PVDF binder solution in N-methyl-2-pyrrolidone (NMP) wasprepared as follows: 1141.44 g of n-methyl pyrrolidone was added to a1-gallon metal can. The solvent was mixed using a 3-inch diameter Cowlesmixing impeller with a rotation rate of 500 RPM. 58.56 g PVDF T-1 fromInner Mongolia 3F Wanhao Fluorochemical Co., Ltd. was added graduallyover 30 minutes to the solvent while maintaining constant agitationusing a 3-inch diameter Cowles mixing impeller with a rotation rate of500 RPM. The solids of the solution were determined to be 4.9% byweight.

Example 18: Preparation of Comparative Slurry Composition in NMP

A comparative electrode slurry was prepared as follows: Slurrycomponents were mixed in a polypropylene cup held in a PTFE adaptorusing a dual asymmetric centrifugal mixer Model ARM-310, made by ThinkyCorporation, Japan. Before preparing the slurry, the binder componentsfrom Comparative Example 17 was agitated by shaking for 30 seconds.24.05 g PDVF binder solution in NMP of Comparative Example 17 and then13.32 g of NMP were added to a 250 ml polypropylene mixing cup. Thecomponents were then mixed using a dual asymmetric centrifugal mixer for1 minute at 2000 RPM. The diluted binder was clear and low viscosity.0.585 g Timcal Super P carbon black from Imerys Graphite & CarbonBelgium SA was added to the diluted binder solution. The components werethen mixed using a dual asymmetric centrifugal mixer for 5 minutes at1000 RPM. A further 0.585 g Timcal Super P carbon black from ImerysGraphite & Carbon Belgium SA was added to the above binder and carbonmixture. The components were then mixed using a dual asymmetriccentrifugal mixer for 5 minutes at 2000 RPM. After mixing, the carbonblack in binder solution was held without mixing for 5 minutes beforeproceeding further. After the above 5 minutes hold period, 8.575 gPhostech P2 Lithium Iron Phosphate (LFP) from Johnson Matthey was addedto the carbon black and binder mix. The components were then mixed usinga dual asymmetric centrifugal mixer for 5 minutes at 500 RPM followed by5 minutes at 1500 RPM. A further 8.575 g Phostech P2 LFP was added tothe LFP, carbon black and binder mix. The components were then mixedusing a dual asymmetric centrifugal mixer for 5 minutes at 500 RPMfollowed by 5 minutes at 2000 RPM. After mixing, the LFP, carbon blackand binder mix was held without mixing for 5 minutes before proceedingfurther. The components were then mixed using a dual asymmetriccentrifugal mixer for 5 minutes at 2000 RPM. After mixing, the LFP,carbon black and binder mix was held without mixing for 5 minutes beforeproceeding further. The components were then mixed using a dualasymmetric centrifugal mixer for 5 minutes at 2000 RPM. After mixing,the LFP, carbon black and binder mix was held without mixing for 5minutes before proceeding further. The components were then mixed usinga dual asymmetric centrifugal mixer for 5 minutes at 2000 RPM.

The solids of the resultant slurry were confirmed to be 35 weight %. Theviscosity of the resultant slurry was measured using a Brookfieldviscometer model LVDV-I+, using spindle number 3 from an LV spindle setwith a rotation rate of 20 RPM. The viscosity was measured immediatelyfollowing mixing (day 1), two days later (day 3), nine days later (day10) and thirteen days later (Day 14). The measured Brookfieldviscosities are shown in Table 2.

TABLE 2 % Viscosity (cP) Example Binder Solids Day 1 Day 3 Day 10 Day 14Example Invention 46.0 4830 3690 3480 3360 15 Example PVDF NMP 35.0 5730Gelled 17

The binder system of the current invention (Example 15) appearsadvantaged compared to PVDF in NMP (Example 17) for managing viscositywithin the range necessary for typical roll-to-roll electrodeapplication utilized in industrial lithium ion battery production, athigher application solids for both power cell and energy cellcompositions. This advantage is more notable with high carbon contentpower cells.

The binder system of the current invention (Example 15) enables shelfstable slurries compared with PVDF/NMP comparative (Example 17) whichform unrecoverable gels within 36-48 hours of slurry preparation.Following gentle agitation, the slurry viscosities remain within a rangenecessary for typical roll-to-roll electrode application utilized inindustrial lithium ion battery production and the out-of-cellperformance is maintained.

Example 19: Preparation of Comparative Electrode

An approximately 6 cm by 30 cm sample of 15-micron thick aluminum foilwas placed onto an AFA-II automatic thick film coater from MTICorporation, wiped with acetone and then wiped with isopropanol. To thecleaned aluminum foil, an aliquot of the slurry of Comparative Example18 was applied as a wet coating using a 10 cm wide doctor blade with ablade gap setting of approximately 145 microns.

Foils coated with wet coatings were dried using a Despatch brand Class Alaboratory box oven with a 2.5″ diameter exhaust duct and a Protocol 3programmable controller using the following ramp-and-soak conditions:Initial set point of 55 degrees centigrade; place the coated foil intothe oven; hold at 55 degrees centigrade for 3 minutes; ramp from 55degrees centigrade to 70 degrees centigrade over 1 minute; hold at 70degrees centigrade for 2 minutes; ramp from 70 degrees centigrade to 90degrees centigrade over 4 minutes; remove the coated foil from the oven.

The dry film thickness (DFT) of the coating on the foil was measuredusing a digital micrometer, taking an average of six measurements, andsubtracting the thickness of uncoated foil to calculate the thickness ofthe coating only. The measured DFT was 41 microns, as shown in Table 3.

A nine square centimeter area of coated foil was weighed using ananalytical balance. The weight of the foil and dried slurry coating wasrecorded to four decimals. A nine square centimeter area of uncoatedfoil was also weighed using an analytical balance. The weight of theuncoated foil was recorded to four decimals. The weight of the driedcoating was calculated by subtracting the weight of the uncoated foilfrom the weight of the coated foil.

The measured volume of the coating was determined by multiplying thearea of the coated foil (nine square centimeters) by the averagemeasured thickness of the coating. The porosity of the dried coated foilwas calculated based on the measured volume of the coating, the measuredmass of the coating, the composition of the coating and the knowndensities of the components. The calculated initial porosity of thecoating as coated was 60%, as shown in Table 3.

The dried coated foils were then pressed using an IMC calender presswith 8-inch diameter rolls, heated to 80° C., with a calendaringpressure of 3000 psi and a line speed of 0.2 meters per minute to atarget porosity of 35%. The pressed film thickness (PFT) of the coatingcalendared to 35% porosity, measured using a digital micrometer, was 25microns, as shown in Table 4.

The flexibility of the calender pressed films was examined as in Example16. The results are included in Table 3.

The peel strength of the calender pressed films were determined as inExample 16. The data from the four strips were analyzed to determine anaverage peel strength and a standard deviation for peel strength in N/mwhich are shown in Table 4.

TABLE 3 % porosity 3 mm DFT as mandrel Example Binder (μm) coatedDefects Bend Example Invention 43 54 none Pass 16 Example PVDF 41 60none Pass 19 NMP

The coated and dried film properties of electrodes produced with thebinder system of the current invention (Example 16) appear advantagedcompared to electrodes produced with PVDF in NMP (Example 19): Thebinder system of the current invention enables flexible electrodes forhigh capacity energy cells, while maintaining initial porosities thatare comparable to PVDF/NMP comparatives. The binder system of thecurrent invention enables improved initial porosities for high carboncontent power cell compared to PVDF/NMP comparatives, while maintainingflexibility.

TABLE 4 Composition (dry weight ratio of active to Electro. ElectricallyPeel conductive Active Conductive PFT strength Failure Example agent tobinder) Material Agent Binder (μm) (N/m) mode Example 88-6-6 LFP Super PInvention 31 42.4 ± 3.8 Mixed* 16 Example 88-6-6 LFP Super P PVDF 2516.6 ± 1.7 Mixed*‡ 19 NMP *some cohesive failure (>200 N/m) onlyadhesive failure region peel strength recorded *‡some cohesive failure(>100 N/m) only adhesive failure region peel strength recorded

All coated electrodes were calendar pressed without film defects ordamage. Peel strength measurements with 88:6:6 (dry weight ratio ofelectrochemically active to electrically conductive agent to binder)power cell compositions were conducted after a cut was made through thecoating to the substrate; otherwise the tape would fail adhesively atthe surface of the pressed coating. Peel strength with binderformulations according to the present invention exceeds NMP comparativesand industry minima and are sufficient for cylindrical and prismaticcells.

Example 20: Preparation of a Dispersant Composition

In a four neck round bottom flask, 375.4 grams of triethylphosphate(TEP) was added and the flask was set up with a mechanical stir blade,thermocouple, and reflux condenser. The flask containing TEP solvent washeated to a set point of 120° C. under a nitrogen atmosphere. A monomersolution containing 228.2 grams of MMA, 244.9 grams of EHA, 87.5 gramsof NVP, 11.5 grams of HEA, and 11.5 grams of MAA was thoroughly mixed ina separate container. A solution of 12.9 grams of Trigonox 131 and 61.1grams of TEP was prepared and added into the flask over 185 minutes.Five minutes after the initiator solution started, the monomer solutionwas started and added over 180 minutes. After both initiator and monomerfeeds were complete, the monomer addition funnel was rinsed with 14.4grams of TEP. Then another solution of 4.3 grams of Trigonox 131 and61.2 grams of TEP was added over 60 minutes. After this second initiatorfeed was complete, the initiator addition funnel was rinsed with 57.9grams of TEP. The reaction was then held at 120° C. for 60 minutes.After the 60-minute hold, the reaction was cooled and poured into asuitable container. The final measured solids of the dispersioncomposition were determined to be 51.16% solids.

Example 21: Preparation of Adhesion Promoter Composition

Triethylphosphate (1473.20 grams) was added to a glass container andheated to 60° C. while stirring on a hotplate. Then, an adhesionpromoter (Solef 5130 PVDF, 69.57 grams) was slowly added over 30 to 60minutes while stirring with a magnetic stir bar until the adhesionpromoter was completely dissolved. Then, once the solution cooled, thedispersant composition of Example 5 (22.146 grams) was added to thesolution and mixed. The measured total non-volatiles content of thisslurry was 5.16% by weight.

Example 22: Preparation of a Binder Dispersion

To a plastic cup was added triethylphosphate (57.64 grams), ethylacetoacetate (17.03 grams), the dispersant dispersion of Example 1(14.22 grams), and the dispersant dispersion of Example 20 (7.03 grams).The mixture was stirred with a dispersing blade until the acrylic wasfully incorporated into the solvent. Then, polyvinylidene fluoridepolymer (PVDF T-1 from Inner Mongolia 3F Wanhao Fluorochemical Co.,Ltd., 58.86 grams) was slowly added over 30 to 60 minutes while stirringwith a dispersing blade until the PVDF was completely dispersed into themixture. The measured total non-volatiles content of this slurry was44.85%, and the ratio of solids of PVDF:Example 1 dispersant:Example 20dispersant was 85:10:5.

Example 23: Preparation of Carbon Dispersion

To a plastic cup was added triethylphosphate (41.99 grams) and ethylacetoacetate (4.09 grams), the binder dispersion from Example 22 (20.63grams), and the adhesion promoter composition from Example 21 (73.48grams). Timcal Super P carbon black from Imerys Graphite & CarbonBelgium SA (9.81 grams) was slowly added over 5 minutes while stirringwith a dispersing blade until the carbon was completely incorporatedinto the dispersion.

Example 24: Preparation of a Slurry Composition

The carbon dispersion from Example 23 (30.00 grams) was added to acontainer. Cathode active powder NMC-111 (60.80 grams) was added in fourportions with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 1000 rpm for 3 minutes to produce the formulatedslurry. The total non-volatiles content of this slurry was 72.0%. Thefinal ratio of NMC-111:Super P:Binder dry solids was 93:3:4.

Example 25: Preparation of Electrodes

Two positive electrodes having different coating thicknesses wereprepared from the slurry composition of Example 24. For each electrode,a wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of the formulated slurry using a doctor blade. This wet filmwas heated in an oven to a maximum temperature of 90° C. for at least 10minutes.

After cooling, the first electrode had an average dry film thickness of51 microns as determined from five measurements with a micrometer. Thedry film was calender-pressed to a film thickness of 34 microns, anddemonstrated a 90-degree peel strength of 129.53 N/m.

After cooling, the first electrode had an average dry film thickness of224 microns was determined from five measurements with a micrometer. Thedry film was calender-pressed to a film thickness of 172 microns, anddemonstrated a 90-degree peel strength of 39.15 N/m.

After cooling, the second electrode had an average dry film thickness of224 microns as determined from five measurements with a micrometer. Thedry film was calender-pressed to a film thickness of 172 microns, anddemonstrated a 90-degree peel strength of 39.15 N/m.

As demonstrated in Example 25, the slurry composition of the presentinvention enables the production of thick coatings.

Example 26: Preparation of Dispersant

Synthesis of (meth)acrylic polymer dispersant with theoretical glasstransition (Tg) of 58° C. The table below lists the synthesis chargecomponents with amounts added:

Amount Ingredients (gram) Charge 1: Methylether of propylene glycol 658Charge 2: methyl methacrylate 1121.1 (premixed) ethyl acrylate 435.9hydroxyl ethyl acrylate 33.2 methacrylic acid 33.15 Charge 3: Tertiaryamyl peroxy 2-ethyl hexyl carbonate 33.8 (premixed) methylether ofpropylene glycol 169.6 Charge 4: Tertiary amyl peroxy 2-ethyl hexylcarbonate 11.9 (premixed) methylether of propylene glycol 169.6 Charge5: methylether of propylene glycol 584.6

To a suitable reaction vessel equipped with a stirrer, reflux condenser,thermometer, heating mantle and nitrogen inlet. Charge 1 was added atambient temperatures. The temperature was then increased to reflux(˜120° C.), at which time the monomer premix of Charge 3 was added over185 minutes. 5 minutes after the start of charge 3, charge 2 was addedover 180 minutes. Upon completion of charge 2 and 3, charge 4 was addedover 60 minutes, followed by a hold for additional 60 minutes at reflux(˜120° C.). Thereafter the reaction temperature was cooled to 40° C. andCharge 5 was added with a subsequent 30 minute hold period. The(meth)acrylic polymer dispersant composition thus formed had atheoretical solid content of 52% by weight.

Example 27: Preparation of a Binder Dispersion

In a plastic container was placed 299.2 grams of triacetin and 123.2grams of the (meth)acrylic copolymer dispersant composition from Example26. The resulting mixture was stirred vigorously using a Cowles bladewhile maintaining a modest vortex. This mixing was continued while 177.6grams of polyvinylidene difluoride powder, PVDF T-1 (Inner MongoliaWanhao Fluorochemical Co., Ltd) was added in small portions. Mixing wascontinued for an additional 20 minutes after all the polyvinylidenedifluoride powder was added. This dispersion had a volume weighted meanparticle size of 351 nm by dynamic light scattering method.

Example 28: Preparation of a Binder Dispersion with Crosslinking Agent

To a plastic container was added 1.05 grams a melamine crosslinkingagent (Cymel 303 available from CYTEC, lot KZKGMP002) and 50.0 grams ofthe binder dispersion from Example 27. This mixture was agitated with adual asymmetric mixer at 2000 RPM for 5 minutes.

Example 29: Preparation of Slurry Composition

To a plastic cup was added Triacetin (8.1 grams) and the binderdispersion from Example 28 (1.77 grams). Conductive carbon LITX 200(0.63 grams) was added in two portions with each sequential blend mixedin a dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.Cathode active powder NMC-111 (19.5 grams) was added in two portionswith each resulting combination sequentially mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 70.0% byweight, and viscosity of this slurry was 4942 cP under a shear rate of10 reciprocal seconds and 760 cP under a shear rate of 100 reciprocalseconds.

It will be appreciated by skilled artisans that numerous modificationsand variations are possible in light of the above disclosure withoutdeparting from the broad inventive concepts described and exemplifiedherein. Accordingly, it is therefore to be understood that the foregoingdisclosure is merely illustrative of various exemplary aspects of thisapplication and that numerous modifications and variations can bereadily made by skilled artisans which are within the spirit and scopeof this application and the accompanying claims.

What is claimed is:
 1. A slurry composition comprising: (a) anelectrochemically active material; and (b) a binder comprising a polymercomprising a fluoropolymer dispersed in an organic medium; wherein theorganic medium has an evaporation rate less than 10 grams per squaremeter per minute, at a dissolution temperature of the fluoropolymerdispersed in the organic medium; wherein the organic medium comprises aprimary solvent and a co-solvent, the primary solvent comprising butylpyrrolidone, a trialkylphosphate, 3-methoxy-N,N-dimethylpropanamide,1,2,3-triacetoxypropane, or combinations thereof, and the co-solventcomprising ethyl acetoacetate, gamma-butyrolacetone, propylebne glycolmethyl ether, dipropylene glycol methyl ether, propylene glycolmonopropyl ether, diethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, or combinations thereof, and wherein the slurrycomposition further comprises a dispersant.
 2. The slurry composition ofclaim 1, wherein the electrochemically active material comprises amaterial capable of incorporating lithium.
 3. The slurry composition ofclaim 2, wherein material capable of incorporating lithium comprisesLiCoO₂, LiNiO₂, LiFePO₄, LiCoPO₄, LiMnO₂, LiMn₂O₄, Li(NiMnCo)O₂,Li(NiCoAl)O₂, carbon-coated LiFePO₄, or a combination thereof.
 4. Theslurry composition of claim 1, wherein the electrochemically activematerial comprises a material capable of lithium conversion.
 5. Theslurry composition of claim 4, wherein the material capable of lithiumconversion comprises sulfur, LiO₂, FeF₂ and FeF₃, Si, aluminum, tin,SnCo, Fe₃O₄, or combinations thereof.
 6. The slurry composition of claim1, wherein the electrochemically active material comprises graphite,silicon compounds, tin, tin compounds, sulfur, sulfur compounds, or acombination thereof.
 7. The slurry composition of claim 1, wherein thefluoropolymer comprises a (co)polymer comprising the residue ofvinylidene fluoride.
 8. The slurry composition of claim 1, wherein thefluoropolymer comprises a polyvinylidene fluoride polymer.
 9. The slurrycomposition of claim 1, wherein the dispersant comprises an additionpolymer.
 10. The slurry composition of claim 9, wherein the additionpolymer has a glass transition temperature less than 100° C.
 11. Theslurry composition of claim 9, wherein the addition polymer has a glasstransition temperature of −50° C. to +70° C.
 12. The slurry compositionof claim 9, wherein the addition polymer comprises an active hydrogengroup.
 13. The slurry composition of claim 12, wherein the activehydrogen group comprises at least one carboxylic acid group.
 14. Theslurry composition of claim 12, wherein the active hydrogen groupcomprises at least one hydroxyl group.
 15. The slurry composition ofclaim 9, wherein the addition polymer comprises a (meth)acrylic polymercomprising constitutional units comprising the residue of methylmethacrylate.
 16. The slurry composition of claim 15, wherein the(meth)acrylic polymer further comprises constitutional units comprisingthe residue of ethylenically unsaturated monomer comprising aheterocyclic group.
 17. The slurry composition of claim 16, wherein the(meth)acrylic polymer comprises at least one epoxy functional group, andthe epoxy functional group is post-reacted with a beta-hydroxyfunctional acid.
 18. The slurry composition of claim 9, wherein thedispersant is prepared by conventional free radical initiated solutionpolymerization of a mixture of ethylenically unsaturated monomersdissolved in a second organic medium.
 19. The slurry composition ofclaim 18, wherein the second organic medium used to prepare thedispersant is the same as the organic medium of the slurry composition.20. The slurry composition of claim 18, wherein the second organicmedium comprises triethylphosphate.
 21. The slurry composition of claim1, wherein fluoropolymer and the dispersant are not bound by a covalentbond.
 22. The slurry composition of claim 9, wherein the slurrycomposition further comprises a cross-linker.
 23. The slurry compositionof claim 1, wherein the dispersant is self-crosslinking.
 24. The slurrycomposition of claim 1, wherein the organic medium has an evaporationrate at 180° C. greater than 80 grams per square meter per minute. 25.The slurry composition of claim 1, further comprising (c) anelectrically conductive agent.
 26. The slurry composition of claim 25,wherein the electrically conductive agent comprises activated carbon,acetylene black, furnace black, graphite, graphene, carbon nanotubes,carbon fibers, fullerene, or combinations thereof.
 27. The slurrycomposition of claim 25, wherein the electrically conductive agentcomprises conductive carbon material having a surface area of 100 m²/gto 1000 m²/g.
 28. The slurry composition of claim 25, wherein theelectrochemically active material (a) is present in amounts of 70 to 99percent by weight; the binder (b) is present in amounts of 0.5 to 20percent by weight and the electrically conductive agent (c) is presentin amounts of 0.5 to 20 percent by weight, based on the total weight ofsolids in the slurry composition.
 29. The slurry composition of claim 1,wherein the slurry composition is substantially free of isophorone. 30.The slurry composition of claim 1, wherein the slurry composition issubstantially free of N-methyl-2-pyrrolidone.
 31. A slurry compositioncomprising: (a) a binder comprising a polymer comprising a fluoropolymerdispersed in an organic medium; and (b) an electrically conductiveagent; wherein the organic medium has an evaporation rate less than 10grams per square meter per minute, at a dissolution temperature of thefluoropolymer dispersed in the organic medium; wherein the organicmedium comprises a primary solvent and a co-solvent, the primary solventcomprising butyl pyrrolidone, a trialkylphosphate,3-methoxy-N,N-dimethylpropanamide, 1,2,3-triacetoxypropane, orcombinations thereof, and the co-solvent comprising ehtyl acetoacetate,gamma-butylrolacetone, propylene glycol methyl ether, dipropylene glycolmethyl ether, propylene glycol monopropyl ether, diethylene gylcolmonobutyl ether, ethylene glycol monohexyl ether, or combinationsthereof; and wherein the slurry composition further comprises adispersant.
 32. An electrode comprising: (a) an electrical currentcollector; and (b) a film formed on the electrical current collector,wherein the film is deposited from the slurry composition of claim 25.33. The electrode of claim 32, wherein the electrical current collector(a) comprises a mesh, sheet or foil comprising copper or aluminum. 34.The electrode of claim 32, wherein the electrode comprises a positiveelectrode.
 35. The electrode of claim 32, wherein the electrodecomprises a negative electrode.
 36. The electrode of claim 32, whereinthe film is cross-linked.
 37. The electrode of claim 32, wherein theelectrical current collector is pretreated with a pretreatmentcomposition.
 38. An electrical storage device comprising: (a) theelectrode of claim 32; (b) a counter electrode; and (c) an electrolyte.39. The electrical storage device of claim 38, wherein the electrolyte(c) comprises a lithium salt dissolved in a solvent.
 40. The electricalstorage device of claim 39, wherein the lithium salt is dissolved in anorganic carbonate.
 41. The electrical storage device of claim 38,wherein the electrical storage device comprises a cell, battery pack,secondary battery, capacitor, supercapacitor, or a combination thereof.